JP2627588B2 - Blue dye synthesized from esthelin and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel blue dye synthesized from eserin and a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, the compound has the following chemical formula:
Blue dye synthesized from Ethelin (C ₂₆ H ₃₁ N ₅ O
₂ ) is known, and this blue pigment is prepared by dissolving 1 g of eserin sulfate in 100 mg of 0.1N aqueous sodium hydroxide solution and allowing to stand for 10 minutes, and adding 500 mg of rubserin obtained to 40 ml of
It can be produced by dissolving in ethanol and passing ammonia gas (Die Farbrea Ktionen des Es
erins, Archiv der Pharmazie, 300. Bd ., 1967/10, 849
-857 pages)

[0003]

Embedded image In addition, as a method for confirming the presence of esthelin salicylate, a method of inducing a blue pigment by adding an aqueous solution of sodium hydroxide to a sample, treating the resulting substance with an ammonia reagent, heating on a water bath, and drying to dryness. (Eighth Revised Japanese Pharmacopoeia First Part Commentary, pages C-783 to C-786, published by Hirokawa Shoten, August 15, 1971).

However, the formation reaction of these blue pigments is extremely slow, and the treatment must be carried out at a relatively high temperature for a relatively long time after adding ammonia.
Also, the yield of the blue dye is extremely poor.

[0005]

SUMMARY OF THE INVENTION The present invention provides a blue pigment which can be easily obtained from Ethelin by performing a simple treatment, and a method for producing the blue pigment.

[0006]

Means for Solving the Problems The blue dye of the present invention can be obtained by reacting Ethelin or a salt of Ethelin and an amino acid under conditions where oxygen is present and the pH is 10 or higher. And having the following physicochemical properties. (a) Molecular formula: C ₂₆ H ₃₂ N ₅ O According to fast atom bombardment mass spectrometry (FABMS. m / z), the measured molecular weight was 430.2604, the calculated value was 430.2607, and (b) the molecular weight when dissolved in methanol. Maximum absorption in the ultraviolet and visible light regions When methanol is neutral, 614 nm (63400), 308 nm (64
00), 248 nm (23500), 234 nm (22700), if methanol is acidic, 581 (60400), 300 (6700), 248 (31100), 230 (2
5300), (c) Maximum wave number in the infrared region (cm ^-1 ) 3410, 1580, 1420, 1295 (d) Rf value: 0.55 (silica gel 60 (Merck) and chloroform: methanol: acetic acid (6: 4: 0.1) (When a mixture is used) (e) Solubility: methanol, ethyl acetate, chloroform,
The compound was soluble in acetone and water and insoluble in hexane. (F) The nuclear magnetic resonance (NMR) spectrum was as follows.

Table 1 ¹³ C and ¹ H NMR spectrum 官能 functional group ¹³ C (ppm) ¹ H (ppm) ━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━━ -CH ₃ 24. 96 1.58 (s, 3H) -CH 3 33.69 3.39 (s, 3H) -CH 2 - 40.12 1.97-2.17 (dt, 2H) -CH 3 40.47 2. 72 (s, 3H)> C <51.61 - -CH 2 - 53.71 2.88 (dd, 2H) -CH = 91.79 6.90 (s, 1H)> CH- 98.23 4. 63 (s, 1H) -CH = 124.51 7.37 (s, 1H)> C = 135.31-> C = 144.30-> C = 150.25-> C = 158.45 -エ Ethelin used in the present invention is represented by the following chemical formula 2]
A type of alkaloid which is contained 0.08 to 0.1% in the seeds (Ca1abar bean) of the climbing plant physostigma, which is native to or grown in the Ca1bar region of western Africa, Is used as

[0008]

Embedded image In addition, examples of the eserin salt used in the present invention include eserin salicylate and eserin sulfate. Eserin salicylate is easily soluble in chloroform, slightly soluble in ethanol, and slightly soluble in water. On the other hand, since Etheline sulfate is easily soluble in water, the use of this Etheline sulfate facilitates the production of the blue pigment of the present invention.

The amino acids used in the present invention are not particularly restricted but include, for example, glycine, leucine, cysteine, alanine, isoleucine, cystine,
Examples include neutral amino acids such as serine, phenylalanine, methionine, valine, tyrosine, asparagine, threonine, and tryptophan, and basic amino acids such as lysine.

[0010] The ratio of the use of Ethelin to the amino acid is 1: 0.1 to 1: 2 by weight, preferably 1: 0.25 to 1: 1.
So that In particular, when the ratio is 1: 0.5, the reaction time is the shortest, and the amount of the blue dye produced is preferred. When the proportion of the amino acid is smaller than 0.5, little change is observed in the reaction time, but the amount of the dye produced tends to decrease, and the proportion of the amino acid is reduced to 0.1.
If it is smaller than this, almost no dye is produced. On the other hand, when the ratio of the amino acid is larger than 2, there is almost no change in the amount of the produced dye, but the reaction time tends to be longer.

In the present invention, when reacting an amino acid with an esterin, an alkaline condition is used. In this case, the pH is 10 or more, preferably 10 to 12, particularly preferably pH 10.
The range is 11 to 11.5. The reason for limiting the pH range in this way is that the higher the pH value, the greater the amount of blue dye produced, whereas the excessively high pH decomposes the produced blue pigment. No dye is produced at pH 9 or lower.

[0012] When a blue pigment is produced by reacting Ethelin with an amino acid, a red pigment is produced as an intermediate product during the reaction. The presence of oxygen is essential when producing this intermediate from eserin, and therefore the reaction of the present invention must be carried out in the presence of oxygen.
At this time, when oxygen is passed, the generation time of the blue dye can be reduced as compared with the case where the above reaction is performed in the atmosphere. However, if the supply of oxygen is continued even after the intermediate product is generated, the oxygen becomes excessive, the intermediate product is decomposed, and the blue pigment is not generated. Therefore, it is preferable to pass the oxygen for a short time, specifically, for about 1 to 10 minutes after the start of the reaction.

The temperature at which Ethelin reacts with the amino acid is 10 to 100 ° C., preferably 30 to 50 ° C., and especially about 40 ° C. for the purpose of producing a large amount of blue dye. Most preferred. The reason that the temperature range is limited in this way is that the reaction rate tends to increase as the temperature conditions during the reaction are increased, but on the other hand, the generated dye is decomposed and the amount of the dye generated is reduced. This is because there is a tendency to decrease.
On the other hand, when the temperature conditions during the reaction are low, it takes a long time to produce a large amount of the dye.

The blue pigment of the present invention is generally produced as follows. Ethelin is added to the solution containing the pH-adjusted amino acid to form a dye, and the water is evaporated under reduced pressure. After acetone is added to the residue to extract the dye, the acetone is evaporated under reduced pressure. The residue is subjected to silica gel column chromatography using Wako Gel C-300 manufactured by Wako Pure Chemical Industries, Ltd., and eluted with a mixed solution of chloroform: methanol (6: 4), and three kinds of the eluted blue dyes are collected.
The collected blue-colored dye was subjected to Toyopearl HW-40 column chromatography (manufactured by Tosoh Corporation), and eluted with a chloroform: methanol (6: 4) mixed solution.
The column was subjected to Sephadex LH-20 column chromatography (Pharmacia), and eluted with methanol.
The eluted main blue dye is collected.

[0015]

According to the present invention, a blue pigment can be synthesized by reacting eserin with a simple processing step in a short time. Further, according to the present invention, a large amount of the blue color can be synthesized.

[0016]

【Example】

Example 1 A NaOH solution was added to a test tube containing 10 ml of a 0.05% glycine solution to obtain a pH of 10.04 and a pH of 1.0.
30, pH 10.60, pH 10.98, pH 11.38, pH 11.6
0, pH 11.92, and then each with Ethelin 0.0.
1 g was added, and glycine and Ethelin were reacted at a temperature of 40 ° C. The result is shown in FIG.

The amount of blue dye produced was determined by measuring the absorbance (color value) of the blue dye at a maximum absorption wavelength of 626.2 nm using a spectrophotometer. Hereinafter, in the other Examples and Comparative Examples, the production amount of the blue dye was measured in the same manner.

[0018]

Example 2 Concentration 0.1 adjusted to pH 10.0 with NaOH
% Ethelin nitrate solution is dispensed into test tubes in 10 ml portions,
After adding 5 mg of each of the following amino acids and stirring, the amino acids were reacted with Ethelin in a 60 ° C. water bath. Table-2 ━━━━━━━━━━━━━━━━━━━━━━━━━━ No. amino acid evaluation ━━━━━━━━━━━━━━━━ １1 alanine ◎ 2 serine ☆ 3 valine ◎ 4 threonine 〇5 leucine 〇6 isoleucine ◎ 7 phenylalanine ８8 tyrosine ９9 tryptophan ◎ 10 cysteine 1111 cystine 1212 methionine 〇13 asparagine 〇14 Lysine 〇 ━━━━━━━━━━━━━━━━━━━━━━━━━━

☆: A beautiful blue color was produced. A: Normal blue color was produced. 〇: A little dark but blue color was produced.

[0020]

Example 3 Eserin was added to 10 ml of each solution adjusted to pH 11.07 by adding NaOH to a 0.05% glycine solution.
0.01 g, room temperature, 40 ° C., 60 ° C., 80 ° C., 10
Glycine and Ethelin were reacted at a temperature of 0 ° C. The result is shown in FIG.

[0021]

Example 4 Eserin was added to 10 ml of each solution adjusted to pH 11.07 by adding NaOH to a 0.05% glycine solution.
Glycine and Ethelin were reacted in a temperature zone of 40 ° C. The result is shown in FIG.

[0022]

Comparative Example 1 The reaction was carried out under the same conditions as in Example 4 except that the pH was changed to 7.10 and 9.05. The result is shown in FIG.

[Brief description of the drawings]

FIG. 1 is a graph showing how the amount of blue pigment produced changes when the pH is changed. Abs on the vertical axis of the graph
Means absorbance.

FIG. 2 is a graph showing how the amount of generated blue pigment changes when the temperature is changed.

FIG. 3 is a graph showing that no blue pigment is produced when the pH is 10 or less.

Continuation of the front page (72) Inventor Shinsuke Imai 1-5-7 Mikitei Sakaecho, Higashiosaka-shi, Osaka House Foods Industry Co., Ltd. (72) Inventor Shiho Sasaki 1-5-7 Mikiteisakae-cho, Higashi-Osaka-shi, Osaka House Food Industry Co., Ltd. (72) Inventor Makiko Mizogami 1-5-7 Mikitei Sakaecho, Higashi Osaka City, Osaka House Food Industry Co., Ltd.

Claims (2)

(57) [Claims] 1. A blue pigment which can be obtained by reacting eserin or a salt of eserin and an amino acid under conditions where oxygen is present and the pH is 10 or more, and which has the following physicochemical properties. (a) Molecular formula: C ₂₆ H ₃₂ N ₅ O (b) Maximum absorption in ultraviolet and visible light regions when dissolved in methanol 614 nm (63400), 308 nm (6400), 248 nm (23500), 234 n
m (22700) (c) Maximum wave number in infrared region (cm ^-1 ) 3410, 1580, 1420, 1295 (d) Rf value: 0.55 (silica gel and chloroform: methanol: acetic acid (6: 4: 0.1) mixed solution is used. (E) Solubility: methanol, ethyl acetate, chloroform,
Soluble in acetone and water and insoluble in hexane 2. A method for producing a blue dye by reacting eserin or an eserin salt and an amino acid under conditions in which oxygen is present and the pH is 10 or more.