JPH02221282A - Photochromic compound - Google Patents

Abstract

NEW MATERIAL:A compound expressed by the formula (R1 represents 1-18C alkyl, 1-5C alkyl-containing arylalkyl, 2-10C alkoxyalkyl, etc.; R2 and R3 represent R1, H, etc.; R4 represents H, 1-18C alkyl, 1-5C alkyl-containing arylalkyl, 1-18C heteroalkyl, etc.; R5 and R7 represent H, OH, 1-9C alkyl, 1-5C alkoxy, halogen, nitro or cyano; R6 represents amino, 1-10C mono or dialkylamino, phenylamino, benzylamino, etc.). EXAMPLE:6-Piperdino-1',3',3'-trimethylspiro ([ 3H-naphtho [ 2,1-b ] -1,4- oxazine-3,2'-piperdine). USE:A photochromic compound which develops a pink color with ultraviolet ray radiation and has superior heat resistance and repeating characteristics. PREPARATION:1,3,3-Trimethyl-2-methylenepiperdine is reacted under heating using a corresponding 1-nitroso-2-naphthol preferably in an 1-3 molar ratio and using piperdine and morpholine preferably in 1-5 molar ratio.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a novel photochromic compound, and more specifically, it develops a pink color when exposed to ultraviolet light,
This invention relates to a photochromic compound that has excellent heat resistance and good repeatability.

[Prior art] Photochromism is a reversible phenomenon in which a material changes color when exposed to light containing ultraviolet rays, such as sunlight or light from a water chrome lamp, and returns to its original color when the light irradiation is stopped and the product is placed in a dark place. Compounds that exhibit this phenomenon are called photochromic compounds.

Among organic photochromic compounds, spirooxazine compounds have good repeating properties, and for example,
-28892 Publication, Special Publication No. 49-48631,
JP-A-55-38284, JP-A-60-1128
80, 1,3,3-trimethylspiro([indoline-2゜3ξ3H-naphtho[2,1-bl-1,
4-oxazine) and its derivatives are disclosed.

However, since most of these compounds develop a blue color when exposed to ultraviolet light, their uses are limited. For practical purposes, variegated tubes in various colors are desired. Unexamined Patent Publication 1986-14
Publication No. 5089 discloses a compound that has absorption in the visible region at a shorter wavelength than these compounds. However, this compound has the disadvantages of a low melting point and low heat resistance.

[Problems to be Solved by the Invention] The present inventors have conducted various studies to eliminate the problems of the prior art described above and improve heat resistance. The present invention was achieved by discovering a photochromic compound with excellent properties and good repeatability.

[Means for Solving the Problem] According to the present invention, general formula (1); [wherein (a) R+ is a linear or branched alkyl group having 1 to 18 carbon atoms, a carbon atom] an arylalkyl group having a linear or branched alkyl group having 1 to 5 carbon atoms; an alkoxyalkyl group having 2 to 10 carbon atoms;
an alkenyl group, phenyl group, benzyl group, mono- or di-substituted phenyl group, or mono- or di-substituted benzyl group having 1 to 10 carbon atoms; (b) R2 and R3 are each independently a group defined in R1; , an alicyclic ring having 5 to IO carbon atoms, norbornyl, adamantyl, bonded between hydrogen atoms or groups existing on the same skeletal carbon atom or between groups on adjacent skeletal carbon atoms (ortho position). can be.

(c) Rn is a hydrogen atom, a straight chain or branched alkyl group having 1 to 18 carbon atoms, an arylalkyl group having a straight chain or branched alkyl group having 1 to 5 carbon atoms, carbon A linear or branched heteroalkyl group having 1 to 18 atoms, or an alkenyl group having 1 to 10 carbon atoms, and (d) Rs and R7 each independently represent a hydrogen atom, a hydroxyl group, a carbon A linear or branched alkyl group having 1 to 9 atoms, an alkoxy group having 1 to 5 carbon atoms, a halogen, a nitro group, or a cyano group; (e) Ra is an amino group, and 1 to 10 linear or branched mono- or dialkylamino groups, phenylamino groups, benzylamino groups.

A photochromic compound is provided which is a mono- or di-substituted phenylamino group or a mono- or di-substituted benzylamino group, a cyclic amino group having 5 to 12 carbon atoms and containing 0 to 3 heteroatoms.

In the photochromic compound represented by the general formula (1), R1, R2 and R3 are linear or branched alkyl groups having 1 to 18 carbon atoms, R4 is a hydrogen atom, and Rs is hydrogen. Number of atoms or carbon atoms is 1~
5 alkoxy group, and R6 has 5 to 12 carbon atoms.
is a cyclic amino group containing 0 to 3 petro atoms, and R7
is a hydrogen atom or an alkoxy group having 1 to 5 carbon atoms, and more preferably R1, R2 and R3 are methyl groups, R4 is a hydrogen atom, and R5 is a hydrogen atom or a methoxy group. It is a photochromic compound in which R6 is a piperidine group or a morpholino group, and R7 is a hydrogen atom or a methoxy group.

A typical example of such a photochromic compound (spironaphthoxazine compound) is 6-piberidino 1
″,3′,3′-)limethylspiro([3H-naphtho[
2,1-bl-1,4-oxazine-3,2'-piperidine), 6-morpholino-1',3',3'-trimethylspiro([3H-naphtho[2,1-bl-1,4 -oxazine-3,2'-piperidine)9-methoxy-6-biberidino1',3',3'-)limethylspiro([3■-naphtho[2,1-bl-1,4-oxazine-3,2 ′−
piperidine).

9-Methoxy-6-morpholino-1',3',3'-trimethylspiro([3H-naphtho[2,1-bl-1,
4-oxazine-3,2'-piperidine), 5-methoxy-6-biperidino 1',3',3''-trimethylspiro([3H-naphtho[2,1-bl-1,
4-oxazine-3,2'-piperidine), 5-methoxy-6-morpholino-1',3',3'-)
Limethylspiro((311-naphtho[2,1-bl-1
, 4-oxazine-3,2'-piperidine).

etc., but are not limited to these.

The photochromic compound according to the present invention is a novel compound that has not been described in any literature, and can be produced, for example, as follows. That is, 1,3.3-
To trimethyl-2-methylenepiperidine, the corresponding l-nitroso-2-naphthol is used in an equimolar ratio or more, preferably at least an equimolar ratio to 3 times the molar ratio, and piperidine or morpholine is used in an equimolar ratio or more, It is preferably used in a molar ratio of equal to or more and up to 5 times the molar ratio, and can be produced by heating the reaction in a suitable solvent such as ethanol, toluene, or trichlene. Also,
In the above method, the corresponding tetrahydropyridinium salt compound is used instead of the 1,3.3-trimethyl-2-methylenepiperidine compound, piperidine or morpholine is used in a molar ratio of 2 times or more, and the reaction is carried out in the same manner as above. It may also be manufactured by The produced photochromic compound is treated with activated carbon, recrystallization method,
It can be purified to a pure product using techniques such as column separation.

The photochromic compound according to the present invention includes benzene,
Common chemicals such as toluene, chloroform, ethyl acetate, methyl ethyl ketone, acetone, ethanol, methanol, isopropyl alcohol, n-butyl alcohol, benzyl alcohol, tetrahydrofuran, dimethyl formamide, dimedyl sulfoxide, dioxane, acetonitrile, methyl cellosolve, ethylene gelcol, etc. It can be dissolved in an organic solvent, and the resulting solution is colorless in the dark, but when it is irradiated with ultraviolet light, it exhibits photochromism in which it develops a pink or purple color.

The photochromink compounds of the present invention can also be used in a colorless or transparent solution prepared from a transparent polymer or copolymer, or a transparent blend thereof, and a suitable organic solvent. It can also be dissolved in the transparent host material polymer described below. Examples of such solutions include polyvinyl acetate-acetone solution, nitrocellulose-acetonitrile solution, polyvinyl chloride-methyl ethyl ketone solution, polymethyl methacrylate-acetone solution, cellulose acetate-dimethylformamide solution, polyvinylpyrrolidone-acetonitrile solution, polystyrene-toluene. Examples include solutions, ethyl cellulose-methylene chloride, and the like.

The photochromic solution or composition is applied to a transparent support such as triacetylcellulose or polyethylene terephthalate or Baryta paper, and when dried,
It is possible to obtain a photochromic material that is colored pink or purple by ultraviolet rays and returns to colorless when the ultraviolet rays are removed.

Such a photochromic material can be prepared by a conventionally known method.
can be built. That is, the photochromic compound of the general formula (I) is used as a resin, oil or fat.

By dissolving, kneading, or coating on a host material such as paper, it can be incorporated into materials of any shape, including solids such as films, lenses, and plates, as well as liquids such as oils and fats and emulsions. There is no particular limitation on the amount of the photochromink compound of the present invention incorporated into the various materials, but it is generally 10-50% by weight, preferably 10-4-50% by weight.
Add 20% by weight.

Photochromic compounds according to the invention can be used, for example, in self-adjusting plastic sunglasses, ski goggles,
Sun visors, window glass, laminated glass, packaging materials, clothing, decorations, car interiors, and paints.

It can be suitably used for ink, nail polish, cosmetics, memory materials, light meters, etc.

[Examples] The present invention will be explained in more detail according to Examples below.
It goes without saying that the technical scope of the present invention is not limited to these Examples.

Example 1 30 g of 1-nitroso-2-naphthol and 30 g of piperidine
A mixture of 150 g of trichloride was heated to 65° C. to dissolve it. After stirring this mixture for an additional 30 minutes,
1.3.3-trimethyl-2-methylenepiperidine 23
．． A mixture of 5 g and 40-g of trichrene was added over 15 minutes, and stirring was continued at 65° C. for an additional 3 hours.

Activated carbon was added to the reaction mixture and J! passed. After almost completely removing trichlene from the obtained filtrate under reduced pressure, ethanol was added and the mixture was allowed to stand in a cold place for about 3 days, and the precipitated crystals were separated by filtration. The crude crystals were dissolved in 5 times the amount of acetone, activated carbon was added thereto, and the heated mixture was passed through and concentrated. The resulting solution was left in a cool place, and the precipitated crystals were collected by filtration, washed with a small amount of cold alcohol, and dried to obtain the desired 6-biperidino 1.
',3',3'trimethylspiro([3H-Nut[2
, 1-b]-1,4-oxazine-3,2'-piperidine) as gray-white crystals were obtained.

The physical properties of the obtained compound were as follows.

Melting point: 175-176℃ Original JLj analysis %l CII
Theoretical value 76.35 8.28 11.13
Actual value 78.16 8.44 11.18■stop
Measurement was carried out in a deuterated chloroform solvent using a JEOL FX-200 spectrometer using 1 ball TMS as an internal standard. The obtained H'-NMR spectrum was as shown in FIG.

It was measured in a deuterated chloroform solvent using a Q Miji NM ball JEOLFX-200 spectrometer. The spectrum of the obtained C1C13-N was as shown in FIG.

Measurements were made using an IR-Spell Digi FTS 15E/D infrared spectrophotometer. IR-spectrum is 3rd
It was as shown in the figure.

Changes in the visible light absorption spectrum in the methanol solution before and after irradiation with Spell ultraviolet rays were measured using an MCPD-1000 ultraviolet-visible spectrophotometer manufactured by Otsuka Electronics. The concentration is 5XIO-
The amount was 5 mol/Q, and the measurement temperature was 25°C. The visible light absorption spectrum obtained was as shown in FIG.

The decolorization rate and half-life were determined from the change in absorbance over time at the maximum visible light absorption wavelength after ultraviolet irradiation.

In a 5×10-' mol/Q methanol solution at 25°C, the decolorization rate was 1.33 sec'' and the half-life was 0.5 sec.

Work Using a XeCl excimer laser as the irradiation light source.

When the coloring ability was examined after 1000 repetitions, 92% of the initial coloring ability was maintained.

Example 2 1-Nitroso-2-naphthol 30. and piperidine 45
．． was added to Trichlene 150- and the mixture was heated to 65°C to dissolve it. After stirring this mixture for an additional 30 minutes.

A mixture (slurry) of 47.2 g of 3.4,5.8-tetrahydro-1,2,3,3-tetramethyl-pyridinium iodide and trichlene 40WjQ was added over 15 minutes, and the mixture was further stirred at 65°C for 3 hours. continued.

Activated carbon was added to the reaction mixture and filtered. Trichlene was almost completely removed from the obtained filtrate under reduced pressure, then ethanol was added and the mixture was allowed to stand in a cold place for about 3 days, and the precipitated crystals were separated. The crude crystals were dissolved in 5 times the volume of acetone, activated carbon was added, and the heated mixture was filtered and concentrated. The resulting solution was left in a cool place, and the precipitated crystals were collected by filtration, washed with a small amount of cold alcohol, and dried to obtain the desired 6-biperidino 1',3.
',3'-)limethylspiro([3tonaphtho[2,1-
568 g of off-white crystals of bl-1,4-oxazine-3,21-piperidine] were obtained.

The physical properties of the obtained compound were the same as in Example 1.

Example 3 - 30 g of nitroso-2-naphthol and 30 g of morpholine
A mixture of 150 all of tricrene was heated to 65° C. to dissolve it. After stirring the mixture for an additional 30 minutes, a mixture of 1,3,3-trimethyl-2-methylenepiperidine 23.5 and trichlene 40- was added over 15 minutes, and stirring was continued for an additional 3 hours at 65°C. .

Activated carbon was added to the reaction mixture and filtered. After almost completely removing trichlene from the obtained filtrate under reduced pressure, ethanol was added and the mixture was allowed to stand in a cold place for about 3 days, and the precipitated crystals were crushed. The crude crystals were dissolved in 5 times the amount of acetone, heated with activated carbon, filtered and concentrated. The resulting solution was left in a cool place, and the precipitated crystals were collected by filtration, washed with a small amount of cold alcohol, and dried to obtain the desired 6-morpholino-1',
3′,3″-trimethylspiro([3■-naphtho[2,
5.5 g of off-white crystals of 1-bl-1,4-oxazine-3,2'-piperidine) were obtained.

The physical properties of the obtained compound were as follows.

Melting point: 157-159°C -CHN Theoretical value 72.79 7.70 11.07 Actual value 72.84 7.52 11.08 H'-NMR Measured in the same manner as in Example 1.

δH (ppm): 0.88 (s, 3'-Me, 3 old, 1
．． 20 (s, 4'-H, III).

1.25 (s, 3'-Me, 3H), 1.80 (m, 5
'-H, IH).

1.91 (m, 5'-H, IH), 1.99 (a, 4'
-11,1 old.

2.24 (s, l'-Me, 3H), 2.80 (m, 6
'-11, IH).

2.87 (Otori, 6″-〇, IH), 3.33 (Shi, Morpholine N-(CH2) 2.4 old, 3.98 (t, Morpholine-0-(CH2) 2.4H), 6 .88(s
, 5-H, IH), 7.35(m, 8-H, ll-
1).

7.43 (s, 2-H, LH), 7.51 (m, 9-H
, IH).

8.03(d,?-H,IH), 8.50(d, 1
0-H, IH) Q 庳二 纳和颜Measurement was carried out in the same manner as in Example 1.

δc (ppm): 21.0 (5ξC), 22.1 (3'
4e), 28.5(3'-Me).

32.8 (4ξC), 39.5 (N-Me), 39
．． 9(Me2-C).

48.2 (8'-C), 53.5 (morpholine-NC2
), 87.3 (morpholine-〇C2), 92.7 (2
'-C), 105.5 (5-C), 119.0 (10b
-C).

121, (10-C), 123. H8-C), 123.
3 (7-C).

123.9 (8a-C), 126.9 (9-C),
132.2 (10a-C).

148.0 (4a-C), 151.1 (2-C), 15
1.3 (8-C) Specimen Measured in the same manner as in Example 1. The maximum wavelength of visible light absorption in the methanol solution was 564 ng+.

'14J! In LILIIL 5×10 −5 mol/Q methanol solution, the decolorization rate at 25° C. was 0.86 sec −1 and the half life was 1.0 seconds.

Using a XeCl excimer laser as the irradiation light source, 10
When we examined the coloring ability after repeating 00 times, the initial coloring ability was 90.
% was retained.

[Brief explanation of the drawing]

FIG. 1 is the Hl-NMR spectrum of the compound of Example 1, and FIG. 2 is its C1C13-N spectrum,
FIG. 3 shows its IRN spectrum, and FIG. 4 shows its visible light absorption spectrum.

Claims (1)

[Claims] General formula (I): ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, (a) R_1 is a straight or branched alkyl group having 1 to 18 carbon atoms, carbon Allyl alkyl group having a linear or branched alkyl group having 1 to 5 atoms, alkoxyalkyl group having 2 to 10 carbon atoms,
is an alkenyl group, phenyl group, benzyl group, mono- or di-substituted phenyl group, or mono- or di-substituted benzyl group having 1 to 10 carbon atoms, and (b) R_2 and R_3 are each independently R_1
an alicyclic ring having 5 to 10 carbon atoms bonded between a hydrogen atom or a group existing on the same skeletal carbon atom or between a group on an adjacent skeletal carbon atom (ortho position); Norbornyl, adamantyl, (c) R_4 is a hydrogen atom, a straight chain or branched alkyl group having 1 to 18 carbon atoms, or a straight chain or branched alkyl group having 1 to 5 carbon atoms. an allyl alkyl group, a linear or branched heteroalkyl group having 1 to 18 carbon atoms, or an alkenyl group having 1 to 10 carbon atoms; Hydrogen atom, hydroxyl group, straight chain or branched alkyl group having 1 to 9 carbon atoms, having 1 to 9 carbon atoms
(e) R_6 is an amino group, a linear or branched mono- or dialkylamino group having 1 to 10 carbon atoms,
Phenylamino group, benzylamino group, mono- or di-substituted phenylamino group or mono- or di-substituted benzylamino group, having 5 to 12 carbon atoms and 0 to 12 heteroatoms
It is a cyclic amino group containing three. ] A photochromic compound represented by