JP3536088B2 - Monoazathia crowned or monoazaoligothioethylene glycolated spirobenzopyran - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel spirobenzopyran compound.

[0002]

2. Description of the Related Art Conventionally, since various compounds such as spirobenzopyran and spirooxazine have a photochromic function, their application as an optical device has been widely studied.

[0003]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a novel compound useful as a photochromic material.

[0004]

Means for Solving the Problems The inventors of the present invention have made extensive studies in view of the above-mentioned problems of the prior art, and as a result, monoazathiacrownated or monoazaoligothioethyleneglycolated compounds, which are novel compounds not described in the literature, have been obtained. It has been found that the spirobenzopyran compound is a photochromic compound having a property that the photochromic property is changed by the presence of metal ions.

That is, the present invention provides the following compounds. Item 1. General formula [1]

[0006]

[Chemical 3]

[In the formula, R represents an alkyl group having 1 to 20 carbon atoms, an aryl group or a heterocyclic group, and n is an integer of 0 to 5. ] Or general formula [2]

[0008]

[Chemical 4]

[In the formula, R is an alkyl group having 1 to 20 carbon atoms.
A group, an aryl group or a heterocyclic group, R ₁Is hydrogen, carbon
Indicates an alkyl group of the numbers 1 to 5, n is an integer of 0 to 5
It ] The spiro benzopyran compound represented by these.

Item 2. A method of using the spirobenzopyran compound according to Item 1 as a photochromic material.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION In the compound represented by the general formula [1] and the compound represented by the general formula [2], R is a linear or branched alkyl group having 1 to 20 carbon atoms. , An aryl group or a heterocyclic group. Preferably methyl, ethyl,
Propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl,
Examples thereof include heptadecyl, octadecyl, nonadecyl, eicosyl and the like. More preferably, it is a C1-C3 alkyl group.

In the compound represented by the general formula [1] and the compound represented by the general formula [2], n is an integer of 0 to 5, preferably 0 to 3.

The method for producing the compound of the present invention will be described below.

Bis (chloroethyl) according to the following reaction formula
Monoazathiacrown ether is synthesized by reacting an amine with an oligothioethylene glycol derivative.

[0015]

[Chemical 5]

[In the formula, n represents an integer of 0 to 5] The solvent used in this reaction is not particularly limited, but tetrahydrofuran (THF), dioxane, ethanol, benzene, dimethylformamide (DMF),
Organic solvents such as dimethyl sulfoxide are exemplified, and dehydrated THF is preferable.

The amount of bis (chloroethyl) amine and oligothioethylene glycol derivative used in this reaction is about 0.5 to 2 moles of oligothioethylene glycol derivative, preferably 1 mole of bis (chloroethyl) amine. Both may be reacted in an equimolar amount.
It is desirable to carry out this reaction under a nitrogen atmosphere.

The reaction temperature of this reaction is 25 to 10
The temperature may be about 0 ° C, preferably about 70 to 80 ° C.
The reaction time may be about 1 to 3 days.

In this reaction, lithium hydroxide is used as a catalyst,
Alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal carbonates such as sodium carbonate and cesium carbonate, alkali metal hydrogen carbonates and the like can be optionally used. Preferably an alkali metal hydroxide,
More preferably lithium hydroxide is used.

Further, bis (chloroethyl) amine is reacted with an oligothioethylene glycol derivative according to the following reaction formula to synthesize monoazaoligothioethylene glycol.

[0021]

[Chemical 6]

[In the formula, R ₁ represents hydrogen, an alkyl group having 1 to 5 carbon atoms, and n represents an integer of 0 to 5] The solvent used in this reaction is not particularly limited, but may be ethanol. , Tetrahydrofuran (THF), dioxane, benzene, dimethylformamide (DMF) and the like are exemplified, and preferably ethanol is exemplified.

The amount of bis (chloroethyl) amine and oligothioethylene glycol derivative used in this reaction is about 1 to 5 mol, preferably 3 mol, of oligothioethylene glycol derivative per 1 mol of bis (chloroethyl) amine. It should be about. This reaction is
It is desirable to carry out under a nitrogen atmosphere.

The reaction temperature of this reaction is 25 to 10
The temperature may be about 0 ° C, preferably about 70 to 80 ° C.
The reaction time may be about 1 to 12 hours. This reaction is carried out using alkali metal hydroxides such as sodium ethoxide, sodium methoxide, lithium hydroxide, sodium hydroxide and potassium hydroxide as catalysts, alkali metal carbonates such as sodium carbonate and cesium carbonate, alkali metal hydrogen carbonates. It can be performed by optionally using a basic compound such as. Preferably alkali metal hydroxides are used, more preferably sodium ethoxide.

The monoazathiacrown ether or monoazaoligothioethylene glycol obtained as described above is reacted with chloromethylspirobenzopyran as shown in the following reaction formula to give a compound of the general formula of the present invention. The compound represented by [1] or the compound represented by the general formula [2] can be obtained.

[0026]

[Chemical 7]

[0027]

[Chemical 8]

[Wherein R is an alkyl having 1 to 20 carbon atoms]
A group, an aryl group or a heterocyclic group, R ₁Is hydrogen, carbon
Indicates an alkyl group of the numbers 1 to 5, n is an integer of 0 to 5
It ] The solvent used in this reaction is not particularly limited
But acetonitrile, dioxane, tetrahydrofuran
Organic solvents such as benzene and benzene are exemplified, and the solvent is preferably tet
Lahydrofuran is exemplified.

Although this reaction can be carried out in the absence of a catalyst, it is preferably carried out in the presence of a catalyst. As the catalyst, a basic compound such as triethylamine, pyridine, sodium carbonate or sodium hydroxide, preferably triethylamine can be used.

The amount of chloromethyl spirobenzopyran used in this reaction with respect to monoazathiacrown ether or monoazaoligothioethylene glycol is about 1 mol or more for the former, preferably 1.5 to about 1 mol for the latter. It may be about 2.5 mol. The amount of the catalyst used may be about 1 mol or more, preferably about 5 to 10 mol, based on 1 mol of monoazathia crown ether or monoaza oligothioethylene glycol. The reaction temperature of this reaction is about 0 to 120 ° C., preferably 80 ° C.
The reaction time may be about 1 hour to 2 days.

The compound of the present invention thus obtained is
It can be easily isolated and purified from the reaction mixture according to a commonly used separation and purification means.

The spirobenzopyran compounds of the present invention include
There are a monoazathiacrown ether and a monoazaoligothioethylene glycol moiety capable of complexing with metal ions, and a spirobenzopyran moiety having a photochromism function is present. Therefore, the spirobenzopyran compound of the present invention has the property that the photochromic property changes due to the presence of metal ions. In particular, the photochromic property is emphasized in the presence of silver ion, and the reverse photochromic property is exhibited in the presence of magnesium ion, zinc ion, lead ion and mercury ion. Therefore, in the presence of the spirobenzopyran compound of the present invention, silver ions are added to emphasize photochromism and magnesium ions, zinc ions, lead ions and mercury ions are added to emphasize reverse photochromism. The photochromism property can be adjusted by adding at least one selected from the group consisting of:

Therefore, the spirobenzopyran compound of the present invention is useful in fields where photochromic materials have been conventionally used and studied, such as light control materials, optical memory materials, optical multiplex recording and liquid crystals. Further, a metal ion detection reagent utilizing photochromic properties corresponding to the complex formation ability with respect to metal ions, preferably a heavy metal ion detection reagent,
It is useful as a silver ion detection reagent, more preferably as a silver ion detection reagent.

[0034]

The present invention will be described below with reference to examples.
The present invention is not limited to these examples.

Example 1 Synthesis of monoazatrithia-12-crown-4-spirobenzopyran (SBP-MAzT12C4) (1) Synthesis of monoazatrithia-12-crown-4

[0036]

[Chemical 9]

In a three-necked flask (300 ml) under a nitrogen atmosphere, 150 ml of dehydrated THF and 288 mg of LiOH (1
2 mmol), bis (2-chloroethyl) amine hydrochloride 357 mg (2 mmol) and dithioethylene glycol 308 mg (2 mmol) were added, and the mixture was heated under reflux for 24 to 72 hours. After allowing the reaction solution to cool, chloroform 200 m
1 and 200 ml of water were added to separate the chloroform layer.
Further, the aqueous phase was extracted with 200 ml of chloroform. Chloroform was distilled off to obtain the desired product. ¹ H-NMR (CDCl ₃ ); δ = 2.7 to 3.0 (16
_{H, m, SCH 2, NCH} 2). (2) Synthesis of monoazatrithia-12-crown-4-spirobenzopyran (SBP-MAzT12C4)

[0038]

[Chemical 10]

Nitrogen atmosphere in a three-necked flask (300 ml)
Lower chloromethyl spirobenzopyran 741 mg (2 mm
ol), monoazatrithia-12-crown-4 to 22
3 mg (1 mmol), triethylamine 1.11 g
(11 mmol), put 100 ml of dehydrated THF, at 6 o'clock
It was heated to reflux. After allowing the reaction solution to cool, THF was distilled off,
The desired product was isolated by GPC. Yield 11%.¹ H-NMR; (CDCl₃, 400 MHz) δ: 1.2
0 (3H, s, CH₃), 1.28 (3H, s, C
H₃), 2.43 (4H, t, J = 7.0Hz, NCH)₂
CH ₂ S), 2.58 (4H, t, J = 7.0Hz, N
CH₂), 2.71 (3H, s, NCH₃) 2.7-
2.8 (8H, m, SCH₂) 3.3-3.5 (2
H, m, PhCH₂), 5.88 (1H, d, J = 1)
0.4 Hz, CH =), 6.55 (1H, d, J = 7.
6Hz, ArH), 6.89 (1H, t, J = 7.4H)
z, ArH), 6.94 (1H, d, J = 10.4H)
z, CH =), 7.08 (1H, d, J = 6.8 Hz,
ArH), 7.20 (1H, t, J = 8.2Hz, Ar
H), 7.94 (1H, s, ArH), 8.17 (1
H, s, ArH).

Example 2 Synthesis of monoazatetrathia-15-crown-5-spirobenzopyran (SBP-MAzT15C5) (1) Synthesis of monoazatetrathia-15-crown-5

[0041]

[Chemical 11]

In a three-necked flask (300 ml) under a nitrogen atmosphere, dehydrated THF 150 ml, LiOH 288 mg (1
2 mmol), bis (2-chloroethyl) amine hydrochloride 357 mg (2 mmol), and trithioethylene glycol 428 mg (2 mmol) were added, and the mixture was heated under reflux for 24-72 hours. After allowing the reaction solution to cool, chloroform 200
ml and 200 ml of water were added and the chloroform layer was separated. Further, the aqueous phase was extracted with 200 ml of chloroform. Chloroform was distilled off to obtain the desired product. ¹ H-NMR (CDCl ₃ ); δ = 2.7 to 3.0 (20
_{H, m, SCH 2, NCH} 2). (2) Synthesis of monoazatetrathia-15-crown-5-spirobenzopyran (SBP-MAzT15C5)

[0043]

[Chemical 12]

Nitrogen atmosphere in a three-necked flask (300 ml)
Lower chloromethyl spirobenzopyran 741 mg (2 mm
ol), monoazatetrathia-15-crown-5 to 2
83 mg (1 mmol), triethylamine 1.11 g
(11 mmol) and 100 ml of dehydrated THF were added, and 36
Heated to reflux for hours. The reaction solution is left to cool and then THF is distilled off.
Then, the target product was isolated by GPC. Yield 44%.¹ H-NMR; (CDCl₃, 400 MHz) δ: 1.1
8 (3H, s, CH₃), 1.27 (3H, s, C
H₃), 2.39 (4H, t, J = 7.8Hz, NCH)₂
CH ₂ S), 2.56 (4H, t, J = 7.6Hz, N
CH₂) 2.8-2.9 (15H, m, SCH₂, NC
H₃) 3.3-3.5 (2H, m, PhCH ₂), 5.
86 (1H, d, J = 10.4 Hz, CH =), 6.5
4 (1H, d, J = 7.6 Hz, ArH), 6.87
(1H, t, J = 7.4Hz, ArH), 6.92 (1
H, d, J = 10.4 Hz, CH =), 7.07 (1
H, d, J = 6.8 Hz, ArH), 7.18 (1H,
t, J = 7.8 Hz, ArH), 7.91 (1 H, s,
ArH), 8.12 (1H, s, ArH).

Example 3 Synthesis of monoazapentathia-18-crown-6-spirobenzopyran (SBP-MAzT18C6) (1) Synthesis of monoazapentathia-18-crown-6

[0046]

[Chemical 13]

In a three-necked flask (300 ml) under a nitrogen atmosphere, 150 ml of dehydrated THF and 288 mg of LiOH (1
2 mmol), bis (2-chloroethyl) amine hydrochloride 357 mg (2 mmol) and tetrathioethylene glycol 548 mg (2 mmol) were added, and the mixture was heated under reflux for 24-72 hours. After allowing the reaction solution to cool, chloroform 20
The chloroform layer was separated by adding 0 ml and 200 ml of water. Further, the aqueous phase was extracted with 200 ml of chloroform. Chloroform was distilled off to obtain the desired product. ¹ H-N
MR (CDCl ₃ ); δ = 2.7 to 3.0 (24H,
m, SCH ₂ , NCH ₂ ). (2) Synthesis of monoazapentathia-18-crown-6-spirobenzopyran (SBP-MAzT18C6)

[0048]

[Chemical 14]

In a three-necked flask (300 ml), under nitrogen atmosphere, 741 mg (2 mm) of chloromethylspirobenzopyran
ol), monoazapentathia-18-crown-6 to 3
43 mg (1 mmol), triethylamine 1.11 g
(11 mmol) and 100 ml of dehydrated THF were added,
Heated to reflux for hours. After the reaction solution was allowed to cool, THF was distilled off and the desired product was isolated by GPC. Yield 35%. ¹ H-NMR; (CDCl ₃ , 400 MHz) δ: 1.1
9 (3H, s, CH ₃ ), 1.27 (3H, s, C
_{H 3), 2.4-2.9 (27H,} m, SCH 2, NCH
₂ , NCH ₃ ) 3.3-3.5 (2H, m, PhC
H ₂ ), 5.87 (1H, d, J = 10.4Hz, CH
=), 6.55 (1H, d, J = 7.6Hz, Ar
H), 6.89 (1H, t, J = 7.4Hz, Ar
H), 6.93 (1H, d, J = 10.8Hz, CH
=), 7.09 (1H, d, J = 7.2 Hz, Ar
H), 7.20 (1H, t, J = 7.6Hz, Ar
H), 7.93 (1H, s, ArH), 8.18 (1
H, s, ArH).

Example 4 Synthesis of 6-monoaza-3,9-dithiaundecane spirobenzopyran (SBP-MAzTDEG) (1) Synthesis of 6-monoaza-3,9-dithiaoundecane

[0051]

[Chemical 15]

200 ml of ethanol was placed in a three-necked flask (500 ml) under a nitrogen atmosphere, and 4.60 g of Na was added.
After dissolving (200 mmol), ethanethiol 7.
44 g (120 mmol) was added, and the mixture was heated under reflux. Bis (chloroethyl) amine hydrochloride 7.14 g (40 mmo
A solution prepared by dissolving l) in 100 ml of ethanol was added dropwise under a nitrogen atmosphere, and the mixture was heated under reflux for 2 hours. After cooling, 100 ml of chloroform and 500 ml of 5 wt% NaOH aqueous solution were added to the reaction solution, the chloroform phase was separated, and the aqueous phase was further extracted with 100 ml of chloroform. Chloroform was distilled off and the desired product was isolated by vacuum distillation. ¹ H-NMR (CDCl ₃ ); δ = 1.27 (6H, t,
_{CH 3), 2.55 (4H,} q, S CH 2 CH 3), 2.
_{70 (4H, q, SCH 2} ), 2.83 (4H, t, N
CH ₂ ). (2) Synthesis of 6-monoaza-3,9-dithiaundecane spirobenzopyran (SBP-MAzTDEG)

[0053]

[Chemical 16]

In a three-necked flask (300 ml), under nitrogen atmosphere, 741 mg (2 mm) of chloromethylspirobenzopyran
ol), 1 of 6-monoaza-3,9-dithiaundecane
93 mg (1 mmol), triethylamine 1.11 g
(11 mmol) and 100 ml of dehydrated THF were added, and the mixture was heated under reflux for 3 hours. After allowing the reaction solution to cool, THF was distilled off,
The desired product was isolated by GPC. Yield 24% ¹ H-NMR; (CDCl ₃ , 400 MHz) δ: 1.1
9 (6H, t, J = 7.4Hz, CH 2 CH 3), 1.2
_{0 (3H, s, CH 3} ), 1.28 (3H, s, C
_{H 3), 2.3-2.5 (8H,} m, SCH 2), 2.5
_{-2.6 (4H, m, NCH 2} ), 2.71 (3H,
s, NCH ₃ ) 3.3-3.5 (2H, m, PhC
H ₂ ), 5.86 (1H, d, J = 10.4Hz, CH
=), 6.54 (1H, d, J = 7.6 Hz, Ar
H), 6.88 (1H, t, J = 7.4Hz, Ar
H), 6.93 (1H, d, J = 10 Hz, CH =),
7.08 (1H, d, J = 7.2 Hz, ArH), 7.
19 (1H, t, J = 7.4 Hz, ArH), 7.92
(1H, s, ArH), 8.17 (1H, s, Ar
H).

Example 5 9-Monoaza-3,6,12,15-tetrathiaheptadecane spirobenzopyran (SBP-MAzTTEG)
(1) Synthesis of 9-monoaza-3,6,12,15-tetrathiaheptadecane

[0056]

[Chemical 17]

250 ml of ethanol was put into a three-necked flask (500 ml) under a nitrogen atmosphere, and 5.75 g (2
After dissolving 50 mmol), 18.30 g (150 mmol) of monoethylthioethylene glycol was added, and the mixture was heated under reflux. Bis (chloroethyl) amine hydrochloride 8.9
A solution prepared by dissolving 25 g (50 mmol) in 150 ml of ethanol was added dropwise under a nitrogen atmosphere, and the mixture was heated under reflux for 4 hours. After cooling down, ethanol was distilled off and chloroform 1
Add 00 ml and 500 ml of 5 wt% NaOH aqueous solution,
The chloroform phase is separated, and the aqueous phase is further chloroform 1.
It was extracted with 00 ml. Chloroform was distilled off, and low-boiling components were distilled off under reduced pressure distillation (100 ° C.) to obtain the desired product. ¹ H-NMR (CDCl ₃ ); δ = 1.27 (6H, t,
_{CH 3), 2.58 (4H,} q, S CH 2 CH 3), 2.
_{70 (12H, q, SCH 2} ), 2.84 (4H, t,
NCH ₂ ). (2) 9-monoaza-3,6,12,15-tetrathiaheptadecane spirobenzopyran (SBP-MAzTT
EG) synthesis

[0058]

[Chemical 18]

In a three-necked flask (300 ml), under nitrogen atmosphere, 741 mg (2 mm) of chloromethylspirobenzopyran
ol), 313 mg (1 mmol) of 9-monoaza-3,6,12,15-tetrathiaheptadecane, 1.11 g (11 mmol) of triethylamine, and dehydrated THF10.
0 ml was added and the mixture was heated under reflux for 3 hours. After the reaction solution was allowed to cool, THF was distilled off and the desired product was isolated by GPC. Yield 27%. ¹ H-NMR; (CDCl ₃ , 400 MHz) δ: 1.0
_{-1.2 (12H, m, CH 3} , CH 2 CH 3), 2.4
_{-2.8 (23H, m, SCH 2} , NCH 2, NC
_{H 3), 3.3-3.5 (2H,} m, PhCH 2), 5.
86 (1H, d, J = 10.4 Hz, CH =), 6.5
5 (1H, d, J = 7.6 Hz, ArH), 6.89
(1H, t, J = 7.6Hz, ArH), 6.93 (1
H, d, J = 10.4 Hz, CH =), 7.08 (1
H, d, J = 7.2 Hz, ArH), 7.20 (1H,
t, J = 7.6 Hz, ArH), 7.93 (1 H, s,
ArH), 8.17 (1H, s, ArH).

Example 6 The photochromic properties of the monoazathiacrowned or monoazaoligothioethyleneglycolated spirobenzopyran compounds synthesized in Examples 1 to 5 were examined. Monoazathiacrownated or monoazaoligothioethylene glycolated spirobenzopyran compound, metal ion (using alkaline earth metal perchlorate (magnesium), heavy metal ion nitrate (silver, lead, mercury, zinc)) 1 x 10
^An acetonitrile solution containing ^-4 mol each was prepared, and the absorption spectrum of the solution left overnight in the dark and the absorption spectrum of the solution irradiated with ultraviolet rays of 365 nm for 3 minutes were measured. S
The absorption spectrum of BP-MAzT12C4 is shown in FIG. In the presence of magnesium ions, the promotion of thermal isomerization by magnesium ions was remarkable, and as a result, reverse photochromism was exhibited. In the presence of heavy metal ions, lead, mercury and zinc ions significantly promote thermal isomerization,
Induced reverse photochromism. On the other hand, silver ions similarly promote thermal isomerization, but only at the time of ultraviolet irradiation, they also promote photoisomerization.

From the above results, the 12-membered ring monoazathiacrowned spirobenzopyran is magnesium ion,
It is clear that it exhibits specific photochromic behavior in the presence of silver, mercury, zinc, and lead ions. A similar tendency was observed for the other compounds obtained in the examples.

[Brief description of drawings]

FIG. 1 is a diagram showing an absorption spectrum of a compound of the present invention before UV irradiation in the presence of metal ions.

FIG. 2 is a diagram showing an absorption spectrum of the compound of the present invention after UV irradiation in the presence of metal ions.

─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Hidefumi Sakamoto 930 Sakaeya, Wakayama Prefecture Wakayama University Faculty of Systems Engineering (72) Inventor Setuko Yajima 930 Sakaeya Wakayama City, Wakayama Faculty of Systems Engineering (56) References JP-A-4-353569 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) C07D 491/107 C09K 9/02 G03C 1/685 CA (STN) REGISTRY (STN)

Claims (2)

(57) [Claims] 1. A general formula [1] [Chemical 1] [In the formula, R is an alkyl group having 1 to 20 carbon atoms or an aryl group.
Alternatively, it represents a heterocyclic group, and n is an integer of 0 to 5. ] Or
General formula [2] [Chemical 2] [In the formula, R is an alkyl group having 1 to 20 carbon atoms or an aryl group.
Or a heterocyclic group, R ₁Is hydrogen, al having 1 to 5 carbon atoms
A kill group is shown and n is an integer of 0-5. ]
Spirobenzopyran compounds. 2. A method of using the spirobenzopyran compound according to claim 1 as a photochromic material.