JP2006343212A - Coloring agent for radiation detection - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a coloring agent for radiation detection for developing a color by sensing a low-level radiation having a low concentration. <P>SOLUTION: This coloring agent for radiation detection for developing a color by irradiation of a radiation includes a phenoxazine-based compound shown by the formula (1). In the formula, X is an oxygen atom or a sulfur atom, and R<SP>11</SP>, R<SP>12</SP>, R<SP>13</SP>, R<SP>14</SP>are the same or different hydrogen atoms or alkyl groups having the carbon number of 1-4, and when X is a sulfur atom, R<SP>15</SP>is a halogen atom, an alkyl group having the carbon number of 1-4 which may be substituted with a halogen atom, an alkoxy group having the carbon number of 1-4 which may be substituted with a halogen atom or a phenoxy group or a naphthoxy group which may be substituted with a nitro group, and when X is an oxygen atom, R<SP>15</SP>is a mono- or di-alkylamino group (in this case, the carbon number of the alkyl group is 1-8), a cycloalkylamino group having the carbon number of 5-7, a piperidyl group or a morpholino group. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a phenoxazine-based compound that develops color upon irradiation with radiation and a coloring material containing a phenazine-based compound.

Radiation is widely used in various industrial fields such as medicine, industry and agriculture. Radiation handling medical facilities, research facilities, and radiation utilization facilities such as nuclear power plants require efficient measures to reduce human exposure and thorough leakage measures. In addition, in a facility that performs sterilization processing using radiation irradiation, it is necessary to accurately grasp the amount of irradiated radiation in a short time.
At nuclear power plants, an area dose rate map is created by regular surveys at fixed points at the entrance to the normal control area, and exposure management is performed by providing information on this dose rate to workers. However, information transmission requires new electrical wiring, and there are cases where it is difficult to respond sensitively to the leakage of radiation.
On the other hand, facilities that use radiation irradiation are required to sense radiation in a wide line area in order to change the radiation dose depending on the object.

In order to respond to such a problem, a radiation detection dye whose color changes (discoloration, color development) in response to radiation has been developed so that it can intuitively cope with radiation leakage. For example, Tokita et al. Disclosed a two-component radiation detection dye such as a combination of an N-sulfonyloxyimide compound and a fluorane dye (J. Photopolym. Sci. Technol., Vol. 14, 221-224). (2001)) (Non-Patent Document 1). Japanese Patent Laid-Open No. 2000-241548 (Patent Document 1) proposes a radiation-sensitive substance whose main component is a leuco dye that exhibits color change even at low-level radiation in a nuclear power plant or the like. Such a detection dye is colored by generating an acid upon irradiation with radiation, thereby detecting the radiation.
However, such detection dyes have problems in grasping the thermal stability and light stability of the dyes, adjustment of the color development sensitivity to acid, compatibility with a carrier such as a polymer, and color development sensitivity when supported on the carrier. In addition, the acid generator also has many problems that must be taken into consideration, such as stability to heat and light, sensitivity to radiation, and compatibility and interaction between the acid generator and the carrier.

  In order to solve such problems of the two-component radiation detection dye, a detection dye composed of a single dye has also been proposed. For example, Irie et al. Have proposed compounds of diarylethenes (Bull. Chem. Soc. Jpn., Vol. 73, No. 10, 2385-2388 (2000)) (Non-patent Document 2). However, these compounds have the property of fading easily by light.

  In addition, the present inventors previously developed a certain compound capable of developing color in response to radiation over a wide range and visually confirming radiation irradiation, that is, phenoxazine represented by the following formula (Formula 5): JP-A-2003-277368 proposes a color former for radiation detection containing a compound of the type.

（式において、Ｒ_１、Ｒ_２、Ｒ_３、Ｒ_４は、水素原子又は同一若しくは異なるアルキル基を示し、Ａは芳香環を示し、ｎは１〜５の整数を示す）

(In the formula, R ₁ , R ₂ , R ₃ and R ₄ represent a hydrogen atom or the same or different alkyl group, A represents an aromatic ring, and n represents an integer of 1 to 5)

J. et al. Photopolym. Sci. Technol. , Vol. 14, 221-224 (2001) Bull. Chem. Soc. Jpn. , Vol. 73, no. 10, 2385-2388 (2000) JP 2000-241548 A JP 2003-277368 A

  Therefore, the present invention provides a compound that develops color at a lower concentration and / or in response to a low level of radiation and can visually confirm the radiation irradiation as compared with known phenoxazine compounds. It is an object of the present invention to provide a color detecting agent for radiation detection.

As a result of further study on the phenoxazine-based compound, the present inventors have found a compound that develops color in response to low-level radiation and can visually confirm irradiation even at low concentrations. The present invention has been completed.
That is, the present invention is a coloring material containing a phenoxazine-based compound that develops color upon irradiation with radiation and a radiation detection label represented by the formula (1) (Chemical formula 6).

（式中、Ｘは、酸素原子又は硫黄原子であり、Ｒ¹¹、Ｒ¹²、Ｒ¹³、Ｒ¹⁴は、それぞれ同一でも異なっていてもよい水素原子又は炭素数１〜４のアルキル基であり、Ｒ¹⁵は、Ｘが硫黄原子のとき、ハロゲン原子、ハロゲン原子で置換されていてもよい炭素数１〜４のアルキル基、ハロゲン原子で置換されていてもよい炭素数１〜４のアルコキシ基若しくはニトロ基で置換されていてもよいフェノキシ基又はナフトキシ基であり、Ｘが酸素原子のとき、モノ若しくはジアルキルアミノ基（この場合アルキル基の炭素数は１〜８である）、炭素数５〜７のシクロアルキルアミノ基、ピペリジル基又はモルホリノ基である）

(In the formula, X is an oxygen atom or a sulfur atom, and R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are each a hydrogen atom or an alkyl group having 1 to 4 carbon atoms which may be the same or different, R ¹⁵ is, when X is a sulfur atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms that may be substituted with a halogen atom, an alkoxy group having 1 to 4 carbon atoms that may be substituted with a halogen atom, or A phenoxy group or a naphthoxy group optionally substituted by a nitro group, and when X is an oxygen atom, a mono- or dialkylamino group (in this case, the alkyl group has 1 to 8 carbon atoms), a carbon number of 5 to 7 A cycloalkylamino group, a piperidyl group or a morpholino group)

  Furthermore, one of the present invention is a coloring material and a radiation detection label containing a phenazine-based compound that develops color upon irradiation with radiation, represented by the following formula (2) (Chemical Formula 7).

（式中、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４は、それぞれ同一でも異なっていてもよい、水素原子、炭素数１〜４のアルキル基、ハロゲン化されていてもよい炭素数１〜４のアルコキシカルボニル基、フェノキシカルボニル基、又はベンジルカルボニル基であり、Ｒ^５は、ハロゲン化されていてもよい炭素数１〜４のアルコキシ基、フェノキシ基、又はベンジルオキシ基であり、Ｒ^６は、炭素数１〜４のアルキル基で置換されていてもよいフェニル基であり、Ｒ^７、Ｒ^８は、水素原子又は炭素数１〜４のアルキル基である）

^{(Wherein, R 1, R 2, R} 3, R 4 are each may be the same or different, a hydrogen atom, C1-4alkyl group, carbon atoms and optionally halogenated 1 to 4 carbon atoms a alkoxycarbonyl group, a phenoxycarbonyl group, or benzyl group, R ⁵ is optionally halogenated alkoxy group having 1 to 4 carbon atoms, phenoxy group, or benzyloxy group, R ⁶ is A phenyl group which may be substituted with an alkyl group having 1 to 4 carbon atoms, and R ⁷ and R ⁸ are a hydrogen atom or an alkyl group having 1 to 4 carbon atoms)

  According to the present invention, it is possible to obtain a phenoxazine-based compound and a color-developing agent and a radiation detection label containing a phenazine-based compound that can develop color in response to radiation in a wide range and can visually confirm irradiation.

The compound represented by the formula (1) of the present invention has a —C (X) R ¹⁵ group (X and R ¹⁵ represent the above-mentioned meanings) at the nitrogen atom at the 10th position, and the 3,7th position. Includes a phenoxazine-based compound having an amino group. In addition, the compound represented by the formula (2) of the present invention also has a —C (O) R ⁵ group (R ⁵ represents the above meaning) at the 10-position nitrogen atom, and 3, 7 Includes phenazine compounds having an amino group at the position. In the compounds of the formulas (1) and (2) of the present invention, the N—C (X) bond or the N—C (O) bond at the 10-position is cleaved by irradiation with radiation, and the respective phenoxazine compounds In addition, a cationic substance of phenazine-based compound is generated, and a color peculiar to those ions is developed, so that radiation can be visually recognized.

In the phenoxazine-based compound represented by the formula (1), R ¹¹ , R ¹² , R ¹³ , and R ¹⁴ are each a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, which may be the same or different, Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, an iso-butyl group, and a sec-butyl group. From the viewpoint of easy availability of raw materials, it is preferable that all of R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are a methyl group or an ethyl group.

In the phenoxazine-based compound represented by the formula (1), R ¹⁵ has a different substituent depending on whether X is a sulfur atom or an oxygen atom. When X is a sulfur atom, R ¹⁵ is a halogen atom, an alkyl group having 1 to 4 carbon atoms that may be substituted with a halogen atom, or an alkoxy group having 1 to 4 carbon atoms that may be substituted with a halogen atom. Or it is the phenoxy group or naphthoxy group which may be substituted by the nitro group.
Here, the halogen atom is a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom. Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n- A butyl group, an iso-butyl group, a sec-butyl group, and a tert-butyl group. Examples of the alkoxy group having 1 to 4 carbon atoms include methoxy group, ethoxy group, n-propoxy group, iso-propoxy group, n- Examples include butoxy, iso-butoxy, sec-butoxy, and tert-butoxy.

When X is an oxygen atom, R ¹⁵ is a mono or dialkylamino group (in this case, the alkyl group has 1 to 8 carbon atoms), a cycloalkylamino group having 5 to 7 carbon atoms, a piperidyl group, or a morpholino group. It is a group. Examples of the alkyl group having 1 to 8 carbon atoms include methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, sec-butyl group, tert-butyl group, and n-hexyl. Group, iso-hexyl group, sec-hexyl group, n-octyl group, iso-octyl group, sec-octyl group, etc., among them, the carbon moiety having 3 to 8 carbon atoms bonded to the carbonyl group. Branched alkyl groups such as iso-propyl group, sec-butyl group, tert-butyl group, sec-pentyl group, sec-hexyl group, sec-octyl group and the like are preferable. A cycloalkylamino group having 5 to 7 carbon atoms is also preferable.

The phenoxazine compound represented by the formula (1) according to the present invention can be produced, for example, by the following known method.
1) When X is a sulfur atom The compound represented by the formula (1) of the present invention can be produced according to the following reaction formula (1) (Chemical formula 8).

（反応式中、Ｒ¹¹、Ｒ¹²、Ｒ¹³、Ｒ¹⁴は、前記の意味を表し、Ｒ¹⁵は、ハロゲン原子、ハロゲン原子で置換されていてもよい炭素数１〜４のアルキル基、ハロゲン原子で置換されていてもよい炭素数１〜４のアルコキシ基若しくはニトロ基で置換されていてもよいフェノキシ基又はナフトキシ基である）

(In the reaction formula, R ¹¹ , R ¹² , R ¹³ , R ¹⁴ represent the above-mentioned meanings, and R ¹⁵ represents a halogen atom, an alkyl group having 1 to 4 carbon atoms which may be substituted with a halogen atom, halogen (It is a phenoxy group or a naphthoxy group optionally substituted with an alkoxy group having 1 to 4 carbon atoms or a nitro group optionally substituted with atoms)

  That is, the phenoxazine-based compound (compound represented by the formula (1) ′) represented by the formula (1) according to the present invention, in which X is a sulfur atom, is a phenol represented by the formula (6) or A phenylchlorothionoformate or naphthylchlorothionoformate represented by the formula (5) produced by the reaction of naphthols and thiophosgene (7), and a phenoxazine dye represented by the formula (3), Bisaminophenoxazines represented by the formula (4) obtained by reduction with a reducing agent such as sodium dithionite in the presence of a base such as sodium hydroxide are converted into sodium hydroxide and sodium bicarbonate. It can be obtained by reacting in the presence of alkali.

2) When X is an oxygen atom The compound represented by the formula (1) of the present invention can be produced according to the following reaction formula (2) (Chemical formula 9).

（反応式中、Ｒ¹¹、Ｒ¹²、Ｒ¹³、Ｒ¹⁴は、前記の意味を表し、Ｒ¹⁵は、モノ若しくはジアルキルアミノ基（この場合アルキル基の炭素数は１〜８である）、炭素数５〜７のシクロアルキルアミノ基、ピペリジル基又はモルホリノ基である）

(In the reaction formula, R ¹¹ , R ¹² , R ¹³ and R ¹⁴ represent the above-mentioned meanings, and R ¹⁵ represents a mono- or dialkylamino group (in this case, the alkyl group has 1 to 8 carbon atoms), carbon A cycloalkylamino group, a piperidyl group or a morpholino group having a number of 5 to 7)

That is, the phenoxazine-based compound (compound represented by the formula (1) ″) represented by the formula (1) according to the present invention in which X is an oxygen atom is a 10-chloro represented by the formula (8). It can be obtained by reacting formylphenoxazine with an amine represented by R ¹⁵ H in the presence of an organic base such as triethylamine.
Examples of the phenoxazine-based compound represented by the formula (1) according to the present invention thus obtained are shown in Table 1 (Table 1) and Table 1 (continued) (Table 2) described later.

In the phenazine-based compound represented by the formula (2), R ¹ , R ² , R ³ , and R ⁴ may be the same or different and each is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or halogenated. An alkoxycarbonyl group having 1 to 4 carbon atoms, a phenoxycarbonyl group, or a benzylcarbonyl group, and the alkyl group having 1 to 4 carbon atoms includes a methyl group, an ethyl group, an n-propyl group, and an iso-propyl group. Group, n-butyl group, iso-butyl group, sec-butyl group and the like. Examples of the alkoxycarbonyl group having 1 to 4 carbon atoms include methoxycarbonyl group, ethoxycarbonyl group, n-propoxycarbonyl group, iso-propoxycarbonyl group, n-butoxycarbonyl group, iso-butoxycarbonyl group, sec-butoxycarbonyl group, Examples of the halogenated alkoxycarbonyl group having 1 to 4 carbon atoms include trichloromethoxycarbonyl group, 2-chloroethoxycarbonyl group, 2,2,2-trichloroethoxycarbonyl group, 1, A 2,2,2-tetrachloroethoxycarbonyl group, a 1,1-dimethyl-2,2,2-trichloroethoxycarbonyl group, etc. are mentioned.

In the phenazine-based compound represented by the formula (2), R ⁵ is an optionally halogenated alkoxy group having 1 to 4 carbon atoms, a phenoxy group, or a benzyloxy group, and may be halogenated. Examples of the alkoxy group having 1 to 4 carbon atoms include methoxy group, ethoxy group, n-propoxy group, iso-propoxy group, n-butoxy group, iso-butoxy group, sec-butoxy group, tert-butoxy group, and trichloromethoxy group. 2-chloroethoxy group, 2,2,2-trichloroethoxy group, 1,2,2,2-tetrachloroethoxy group, 1,1-dimethyl-2,2,2-trichloroethoxy group, and the like.

In the phenazine-based compound represented by the formula (2), R ⁶ is a phenyl group which may be substituted with an alkyl group having 1 to 4 carbon atoms, and includes a phenyl group, a methyl group, an ethyl group, n- Examples thereof include a phenyl group substituted with an alkyl group such as a propyl group, an iso-propyl group or an n-butyl group.
In the phenazine-based compound represented by the formula (2), R ⁷ and R ⁸ are a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and are a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, Examples include n-butyl group, iso-butyl group, sec-butyl group and the like.

  The phenazine compound represented by the formula (2) according to the present invention can be produced, for example, by the following known method represented by the reaction formula (3) (Chemical Formula 10).

（反応式中、Ｒ^１’、Ｒ^２’、Ｒ^３’、Ｒ^４’は、それぞれ同一でも異なっていてもよい、水素原子又は炭素数１〜４のアルキル基を表し、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^７、Ｒ^８は、前記の意味を表す）

(In the reaction formula, R ^{1 ′} , R ^{2 ′} , R ^{3 ′} , and R ^{4 ′} each represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, which may be the same or different, and R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ represent the above meanings)

That is, the phenazine-based compound represented by the formula (2) according to the present invention has a phenazine dye represented by the formula (9), such as sodium dithionite in the presence of a base such as sodium hydroxide. Obtained by reacting the compound represented by the formula (10) obtained by reduction with a reducing agent and the chloroformate represented by the formula (11) in the presence of a base such as sodium hydroxide. It is done. In this reaction, when NR ^{1 ′} R ^{2 ′} and / or NR ^{3 ′} R ^{4 ′} is NH ₂ , it reacts with the chloroformate of formula (11) to produce NR ¹ R ² and / or NR ³ R ^4. is a NHCOR ^5.
Examples of the phenazine-based compound represented by the formula (2) according to the present invention thus obtained are shown in Table 2 (Table 3) described later.

  The phenoxazine compound represented by the formula (1) and the phenazine compound represented by the formula (2) according to the present invention are dissolved or dispersed in a solvent or a carrier and irradiated with radiation such as γ rays. Then, in any compound, the N-CO or N-CS bond at the 10-position is cleaved, and the oxidation reaction proceeds with oxygen contained in the air, the solvent, or the carrier to generate a phenoxazine dye and a phenazine dye, respectively. Since it develops in a color peculiar to each cation, radiation irradiation can be visually confirmed.

  For example, when the phenoxazine-based compound represented by the formula (1) according to the present invention is dissolved in a solvent such as acetonitrile, and the colorless solution is irradiated with γ rays, the above chromophore is generated and becomes blue. Color develops (λmax = about 644 nm). In addition, when the phenazine-based compound represented by the formula (2) according to the present invention is dissolved in a solvent such as acetonitrile, and the colorless solution is irradiated with γ rays, a chromophore is generated, and yellow (for example, λmax = 460 nm) and reddish purple (λmax = 568 nm), etc.

When any compound according to the present invention is dissolved or dispersed in a solvent or a carrier and irradiated with radiation, the absorbance at λmax increases in proportion to the increase in absorbed dose, and the phenoxazine type of formula (1) In the compound, when X is a sulfur atom, the absorbed dose is 40 Gy at a concentration of 2.5 × 10 ⁻⁴ M, and when X is an oxygen atom, about 2 Gy at a concentration of 2.5 × 10 ⁻⁴ M Visible with absorbed dose. Moreover, the phenazine-type compound of Formula (2) can be visually recognized at a concentration of 2.5 × 10 ⁻⁴ M and an absorbed dose of about 10 Gy.
In addition, since the absorbance at λmax is proportional to the compound concentration, it can be visually confirmed even at a lower absorbed dose by increasing the concentration of the compound.

Accordingly, both the phenoxazine compound of formula (1) and the phenazine compound of formula (2) according to the present invention are dissolved in a solvent or dispersed in a carrier to form a coloring material that develops color upon irradiation with radiation. be able to.
Examples of the solvent include alcohols, acetonitrile, tetrahydrofuran, and ethyl acetate. Examples of the carrier include polymers such as PVA, PMMA, PET, and polysilane, liquid crystals, and amorphous materials. As the solvent, acetonitrile is particularly preferable.
Furthermore, both the phenoxazine compound of formula (1) and the phenazine compound of formula (2) according to the present invention can be used as a radiation detection label. The radiation detection label according to the present invention is prepared by dissolving a phenoxazine compound of the formula (1) or a phenazine compound of the formula (2) according to the present invention together with a polymer such as PVA, PMMA, PET, and polysilane. Or a phenoxazine compound of the formula (1) or a phenazine compound of the formula (2) according to the present invention is dissolved in a polymer such as PVA, PMMA, PET, or polysilane melted at a high temperature. It can be easily obtained by a method such as molding.

The configuration and effects of the present invention will be specifically described below with reference to examples.
Example 1 (Production of 3,7-bis (diethylamino) -10- (p-chlorophenoxythiocarbonyl) phenoxazine) (Production of Compound No. 1106)
13 ml of hexane in which 1.21 g (10.53 mmol) of thiophosgene was dissolved was added to a 50 ml three-necked flask purged with argon. To this, 10 ml of water in which 1.20 g (9.29 mmol) of p-chlorophenol and 0.25 g (6.25 mmol) of sodium hydroxide were dissolved was slowly added dropwise at room temperature. After completion of dropping, the mixture was stirred at room temperature for 5 hours. Then, liquid separation operation was performed and the hexane layer containing p-chlorophenyl chlorothionoformate was fractionated. The hexane layer was used immediately for the next reaction.
Under a nitrogen atmosphere at room temperature, 1.46 g (4.06 mmol) of 3,7-bis (diethylamino) phenoxazinium chloride was dissolved in 50 ml of water. Thereafter, 50 ml of toluene was added and stirred for about 10 minutes, and then 1.39 g (8.05 mmol) of sodium dithionite, 0.38 g (9.48 mmol) of sodium hydroxide and 0.52 g (6.16 mmol) of sodium bicarbonate. 50 ml of water in which the solution was dissolved was added and protected from light. After a reduction reaction by stirring for 30 minutes, about 15 ml of a hexane solution containing the above crude p-chlorophenylchlorothionoformate was slowly added dropwise at room temperature. After completion of dropping, the mixture was stirred at room temperature for 15 hours. Then, liquid separation operation was performed and the toluene layer was fractionated. After drying over anhydrous sodium sulfate, toluene was distilled off. Preparative TLC was performed using the obtained residue, and then Soxhlet extraction was performed. The residue was recrystallized from methanol to obtain 313.6 mg (0.63 mmol) of the objective compound 3,7-bis (diethylamino) -10- (p-chlorophenoxythiocarbonyl) phenoxazine as colorless needle crystals (yield). Rate 15.6%). The physical properties are shown in Table 1 (Table 1).

Example 2 (Production of 3,7-bis (diethylamino) -10- (N-cyclohexylcarbamoyl) phenoxazine) (Production of Compound No. 1102)
Under an argon atmosphere, 289 mg (0.745 mmol) of 3,7-bis (diethylamino) -10-chloroformylphenoxazine, 297 mg (3.00 mmol) of cyclohexylamine and 0.3 ml of triethylamine were added to 10 ml of acetone. The solution was refluxed with stirring for 2 hours and 30 minutes, and then water was added to dissolve the hydrochloride, followed by extraction with 10 ml of toluene. The toluene layer is washed with water and dried over anhydrous sodium sulfate, the toluene is distilled off, and the residue is subjected to low-temperature recrystallization twice with methanol, whereby the target compound (3,7-bis (diethylamino) -10- (N- Cyclohexylcarbamoyl) phenoxazine (61.3 mg) was obtained as a purple-white columnar crystal (yield 18.3%), and the physical properties are shown in Table 1 (Table 1).

Example 3 (Production of 3,7-bis (diethylamino) -10- (N-sec-butylcarbamoyl) phenoxazine) (Production of Compound No. 1103)
Under an argon atmosphere, 621 mg (1.60 mmol) of 3,7-bis (diethylamino) -10-chloroformylphenoxazine, 350 mg (4.80 mmol) of sec-butylamine and 0.3 ml of triethylamine were added to 10 ml of acetone. The solution was refluxed with stirring for 2 hours and 30 minutes, and then water was added to dissolve the hydrochloride, followed by extraction with 10 ml of toluene. The toluene layer is washed with water, dried over anhydrous sodium sulfate, toluene is distilled off, and the residue is recrystallized with methanol at low temperature to give the desired compound 3,7-bis (diethylamino) -10- (N-sec-butylcarbamoyl). ) 282 mg of phenoxazine was obtained as bluish white columnar crystals (yield 41.4%). The physical properties are shown in Table 1 (Table 1).

Example 4 (Production of 3,7-bis (2,2,2-trichloroethoxycarbonylamino) -2,8-dimethyl-5-phenyl-10- (2,2,2-trichloroethoxycarbonyl) phenazine)) Production of Compound No. 1201)
Under an argon atmosphere, 373 mg (1.03 mmol) of 3,7-amino-2,8-dimethyl-5-phenylphenazinium chloride (Saflaneine O) was dissolved in 20 ml of water, and 20 ml of toluene was added. Next, 20 ml of water in which 808 mg (20.2 mmol) of sodium hydroxide, 811 mg (4.66 mmol) of sodium dithionite and 510 mg (6.07 mmol) of sodium hydrogen carbonate were dissolved was added and stirred vigorously. When the aqueous layer turned colorless, a solution prepared by dissolving 2037 mg (9.61 mmol) of 2,2,2-trichloroethyl chloroformate in 30 ml of toluene was dropped into this reaction solution using an isobaric dropping funnel. After stirring overnight, the toluene layer was separated. The toluene layer was washed with water and dried over anhydrous sodium sulfate, and then toluene was distilled off to obtain a black residue. This residue was dissolved in a mixed solvent of toluene and ethyl acetate (100: 7.5), this solution was applied to a preparative TLC (silica gel), and developed with the previously used mixed solvent of toluene and ethyl acetate. Then, the spot which seems to be a target object was shaved and Soxhlet extraction was carried out with ethyl acetate. Ethyl acetate was distilled off, and recrystallization with methanol gave 3,7-bis (2,2,2-trichloroethoxycarbonylamino) -2,8-dimethyl-5-phenyl-10- (2 , 2,2-Trichloroethoxycarbonyl) phenazine (102.5 mg) was obtained as a white powder (yield 12%). Physical property values are shown in Table 2 (Table 2).

Example 5 (Production of 3,7-bis (dimethylamino) -5- (4-methylphenyl) -10- (2,2,2-trichloroethoxycarbonyl) phenazine) (Production of Compound No. 1203)
Under an argon atmosphere, 756 mg (1.93 mmol) of 3,7-bis (dimethylamino) -5- (4-methylphenyl) phenazinium chloride was dissolved in 40 ml of water, and 40 ml of toluene was added. Next, 40 ml of water in which 416 mg (10.4 mmol) of sodium hydroxide, 2204 mg (6.02 mmol) of sodium dithionite and 889 mg (10.6 mmol) of sodium hydrogen carbonate were dissolved was added and stirred vigorously. When the aqueous layer turned colorless, a solution prepared by dissolving 1283 mg (6.05 mmol) of 2,2,2-trichloroethyl chloroformate in 30 ml of toluene was dropped into the reaction solution using an isobaric dropping funnel. After stirring overnight, the toluene layer was separated. The toluene layer was washed with water and dried over anhydrous sodium sulfate, and then toluene was distilled off to obtain a reddish purple solid. This solid was dissolved in a mixed solvent of toluene and ethyl acetate (100: 7.5), this solution was applied to a preparative TLC (silica gel), and developed with the previously used mixed solvent of toluene and ethyl acetate. Then, the spot which seems to be a target object was shaved and Soxhlet extraction was carried out with ethyl acetate. Ethyl acetate was distilled off, and recrystallization with methanol gave 3,7-bis (dimethylamino) -5- (4-methylphenyl) -10- (2,2,2-trichloroethoxycarbonyl) as the target compound. 33.2 mg of phenazine was obtained as a pale yellowish white powder (yield 3.2%). Physical property values are shown in Table 2 (Table 2).

Example 6 (γ-ray irradiation test of compound according to the present invention)
Irradiation test of irradiating a predetermined amount of γ-rays using ⁶⁰ Co as a radiation source to a distilled acetonitrile solution (compound concentration 2.5 × 10 ⁻⁴ M) of the compound according to the present invention manufactured in Examples 1 to 5 and the like Was done. The color development state of each solution by γ-ray irradiation was measured by UV spectrum, and the absorbance with respect to γ-ray absorbed dose (unit: Gy) at λmax is shown in Table 1. Moreover, when the color development state was visually observed, the compounds of Examples 1 to 5 could be visually recognized from the absorbed doses of 40 Gy, 2 Gy, 2 Gy, 10 Gy, and 10 Gy, respectively.

Claims (4)

A coloring material for radiation detection which contains a phenoxazine compound represented by the formula (1) (Chemical formula 1) and develops color upon irradiation with radiation.

(In the formula, X is an oxygen atom or a sulfur atom, and R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are each a hydrogen atom or an alkyl group having 1 to 4 carbon atoms which may be the same or different, R ¹⁵ is, when X is a sulfur atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms that may be substituted with a halogen atom, an alkoxy group having 1 to 4 carbon atoms that may be substituted with a halogen atom, or A phenoxy group or a naphthoxy group optionally substituted by a nitro group, and when X is an oxygen atom, a mono- or dialkylamino group (in this case, the alkyl group has 1 to 8 carbon atoms), a carbon number of 5 to 7 A cycloalkylamino group, a piperidyl group or a morpholino group) A radiation detection label that contains a phenoxazine compound represented by the formula (1) (Chemical Formula 2) and develops color upon irradiation with radiation.

(In the formula, X is an oxygen atom or a sulfur atom, and R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are each a hydrogen atom or an alkyl group having 1 to 4 carbon atoms which may be the same or different, R ¹⁵ is, when X is a sulfur atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms that may be substituted with a halogen atom, an alkoxy group having 1 to 4 carbon atoms that may be substituted with a halogen atom, or A phenoxy group or a naphthoxy group optionally substituted by a nitro group, and when X is an oxygen atom, a mono- or dialkylamino group (in this case, the alkyl group has 1 to 8 carbon atoms), a carbon number of 5 to 7 A cycloalkylamino group, a piperidyl group or a morpholino group) A coloring material for radiation detection, which contains a phenazine compound represented by the formula (2) (Chemical formula 3) and develops color upon irradiation with radiation.

^{(Wherein, R 1, R 2, R} 3, R 4 are each may be the same or different, a hydrogen atom, C1-4alkyl group, carbon atoms and optionally halogenated 1 to 4 carbon atoms a alkoxycarbonyl group, a phenoxycarbonyl group, or benzyl group, R ⁵ is optionally halogenated alkoxy group having 1 to 4 carbon atoms, phenoxy group, or benzyloxy group, R ⁶ is A phenyl group which may be substituted with an alkyl group having 1 to 4 carbon atoms, and R ⁷ and R ⁸ are a hydrogen atom or an alkyl group having 1 to 4 carbon atoms) A radiation detection label that contains a phenazine compound represented by the formula (2) (Chemical Formula 4) and develops color upon irradiation with radiation.

^{(Wherein, R 1, R 2, R} 3, R 4 are each may be the same or different, a hydrogen atom, C1-4alkyl group, carbon atoms and optionally halogenated 1 to 4 carbon atoms a alkoxycarbonyl group, a phenoxycarbonyl group, or benzyl group, R ⁵ is optionally halogenated alkoxy group having 1 to 4 carbon atoms, phenoxy group, or benzyloxy group, R ⁶ is A phenyl group which may be substituted with an alkyl group having 1 to 4 carbon atoms, and R ⁷ and R ⁸ are a hydrogen atom or an alkyl group having 1 to 4 carbon atoms)