JPH0549670B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Technical Field] The present invention relates to a novel spicrysporic acid (4,5-dicarboxy-4-
pentadecanolide) derivatives.

[Prior art]

In recent years, the process of utilizing biological factors has been called biotechnology, and its development has been remarkable, with many important technologies emerging. For example, useful organic acids and polyhydric alcohols with unique structures have been isolated from various bacterial cell products obtained through fermentation, cultivation, and extraction of carbohydrates, fatty acids, lipoproteins, and phospholipids, and have attracted attention. has been done. In particular, substances that have both a carboxyl group and a lactone ring, such as spicrisporic acid, are multifunctional substances. For example, sodium or amine salts of them are called biosoaps, which can be dispersed, emulsified, solubilized, Shows surface activity such as wetting and penetration,
It is industrially valuable (Japanese Patent Application Laid-open Nos. 58-29130 and 60-31821).

By deriving spicrisporic acid into a pigment-structured compound, a unique compound with high added value can be obtained, which has surface-active properties as well as coloring properties, staining properties, fluorescence, and affinity for living tissues due to its pigment structure. However, such a compound has not been proposed so far.

〔the purpose〕

An object of the present invention is to provide a novel spicrisporic acid derivative into which a dye structure has been introduced.

[Structure] According to the present invention, a spicrisporic acid derivative selected from the following general formulas (), (), and () is provided.

General formula () General formula () General formula () In the above formula, M is hydrogen or a salt-forming cation. In this case, examples of salt-forming cations include alkali metal ions such as sodium and potassium, alkaline earth metal ions such as calcium, polyvalent metal ions such as aluminum, ammonium ions, organic ammonium ions, and the like.

R ¹ and R ² are hydrogen, an alkyl group or an alkylimino group.

Y is hydrogen, halogen, hydroxyl group or alkyl group.

Z is hydrogen, halogen, hydroxyl group or alkyl group. X is an anion, and examples thereof include various acid anions such as halogen, sulfonic acid, sulfuric acid, and alkyl sulfuric acid.

Note that the alkyl group described above may further have a substituent such as a halogen or a hydroxyl group.

Next, the method for synthesizing the compound of the present invention will be described in detail.

In the present invention, spicrisporic anhydride is used as a starting material.

(1) Synthesis of compound of general formula () A compound of general formula () is obtained by reacting spicrisporic anhydride with two molecules of aminophenol. The reaction in this case proceeds as follows, and a compound of general formula () is produced via intermediates () and ().

This reaction was carried out in order to avoid thermal decomposition of spicrisporic anhydride and aminophenol.
The reaction temperature is 180°C or lower, preferably 140-145°C. The reaction pressure is not limited, and the reaction can be carried out at any pressure such as normal pressure, reduced pressure, or increased pressure, and under an inert gas atmosphere such as nitrogen. Further, in order to make the reaction proceed smoothly and increase the yield, it is preferable to thoroughly melt and mix the reaction materials while stirring, or to coexist an inert organic solvent. In this case, a hydrocarbon or halogenated hydrocarbon solvent can be used as the inert solvent. Furthermore, the reaction can be accelerated by adding a small amount of an inorganic acid such as sulfuric acid as a catalyst.

(2) Synthesis of the compound of the general formula () The compound of the general formula () is made by adding an acid such as sulfuric acid or hydrochloric acid to the compound of the general formula () to make it acidic.
It can be obtained by opening a lactone ring.

(3) Synthesis of compound of general formula () This compound can be obtained in the same manner by using a polyhydric phenol such as resorcinol in place of the aminophenols in the above reaction.

〔effect〕

The spicrisporic acid derivative according to the present invention has a long-chain hydrocarbon group and a carboxyl group derived from spicrisporic acid, and has a surfactant effect, and also has a xanthene-based pigment structure in its molecule. colorability, dyeability,
It also has properties such as fluorescence. Therefore, the spicrisporic acid derivative of the present invention can be advantageously used as a dye as well as a surfactant.

〔Example〕

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

Note that all parts shown below are parts by weight.

Example 1 A crude product of spicrisporic acid was recrystallized from water-ethanol to obtain a purified product in the form of colorless needle-like crystals (melting point: 146°C). This purified product is heated to 170-180℃ for about 1 hour.
The anhydride (melting point: 41° C.) was obtained almost quantitatively by heating and dehydrating under conditions of 1 to 2 Torr. The analysis results of this anhydride were as follows.

[Elemental analysis results]

Measured value: C; 65.78 H; 8.44 Calculated value: C; 65.93 H; 8.41 [IR analysis result] Absorption at 1840 (cm ^-1 ) and 1760 by acid anhydride group,
Absorption at 1710 due to carboxyl group and absorption at 1665 due to ethylene bond (>=<) were confirmed.

Next, to 3.1 parts of this spicrysporic anhydride,
3-diethylaminophenol (purity 99.1%)
3.3 parts were added (molar ratio = 1:2), and both were heated and melted while stirring uniformly. In this case, the melting temperature is 140-145 °C, and the reaction mixture reaches this temperature by about 1.5 °C.
Holds time. The reaction condensate thus obtained exhibited a dark purple-red paste form at room temperature.

Add 5% aqueous sodium hydroxide solution to this reaction condensate.
Add 40 parts, filter out impurities (alkali-soluble parts) as necessary, and prepare the spicrysporic acid derivative () having a pigment structure (in the general formula (),
^R1 , ^R2 : ethyl group, Y: hydrogen, M: sodium)
I got it.

Note that extraction and separation using esters such as ethyl acetate could be applied to the separation of this derivative (). Moreover, this derivative () showed solubility in methanol, acetone, carbon tetrachloride, and toluene. A methanol solution of this derivative () exhibited a purple-red color and λmax: 551 (fluorescence 650 nm).

The structure of the derivative () was determined by IR analysis as follows:
2950 (cm ^-1 ) (long chain alkyl), 1810, 1770 (lactone), 1720 (carboxyl group), 1620 (aromatic ring or >
This was confirmed by the presence of absorption of =<). In addition, the presence of a peak of long-chain alkyl groups was also observed in NMR analysis.

Next, when the derivative () is made acidic by adding an aqueous solution of hydrochloric acid or sulfuric acid, an oil-soluble purple-red dye cationic salt derivative () (in the general formula (), R ¹ , R ² : ethyl Group, Y: hydrogen,
M: sodium, X: halogen) and its solution were obtained. An aqueous hydrochloric acid solution of this derivative () is
It showed light absorption at λmax571 (fluorescence 589 nm). In addition, this derivative () is a surface active substance with an amphipathic structure, and the surface tension of its aqueous solution is
As shown in the figure, it showed a tendency to decrease significantly.

In addition, in the above synthesis agent, o-diethylamino-p instead of 3-diethylaminophenol
A similar reaction with -cresol or other substituted aminophenols yields red-colored oil-soluble dyes.

Example 2 Spicrisporic acid anhydride and resorcinol are heated and mixed (130 to 135°C) with a small amount of sulfuric acid at a molar ratio of 1:2. After the reaction, the mixture is washed with water until it becomes neutral to give an orange-red colored spicrisporic acid. The derivative () was obtained. This product is insoluble in carbon tetrachloride and xylene, but soluble in water, aqueous alkaline solutions, methanol, acetone, and the like. In addition, a dilute alkaline solution (1:500) of this product emitted green fluorescence similar to fluorescein when exposed to ultraviolet light. Furthermore, this product reacted with metal halides such as barium chloride and aluminum chloride to produce metal salts (lakes).

Example 3 Bromine was added dropwise to an alcoholic or acidic solution of the derivative (2) shown in Example 2 and reacted to obtain a reddish fluorescent dye similar to eosin dye.

Example 4 The derivative () and cationic salt of Example 1 exhibit the properties of basic dyes, and their methanol-containing acidic aqueous solution dyes fibers such as nylon, wool, and silk, and produces a wine color. gave dyeing.

Example 5 50 parts of the derivative () shown in Example 1, 10 parts of an acidic color developer, and 40 parts of ethylene glycol were mixed,
Recording inks, fluorescent inks, and oil-based colorants for various accessories were obtained.

[Brief explanation of the drawing]

FIG. 1 is a graph showing the relationship between the concentration and surface tension of an aqueous solution of the derivative of the present invention.

Claims (1)

[Claims] 1. A spicryspor derivative selected from the following general formulas (), (), and (). General formula () General formula () General formula () (In the above formula, M is hydrogen or a salt-forming cation,
R ¹ and R ² are hydrogen, an alkyl group, or an alkylimino group, Y is hydrogen, halogen, hydroxyl group, or alkyl group, Z is hydrogen, halogen, hydroxyl group, or alkyl group, and X is an anion)