JPH02134386A - Tetraazaporphyrin compound - Google Patents

Abstract

NEW MATERIAL:A compound in which 1 or 2 molecules of a naphthalene derivative expressed by formula II (Y and Z represent O or NH) are added to a tetraazaporphyrin compound expressed by formula I [M represents group Ia, IIa and IIIa atom of the periodic table or transition metal; R<1> and R<2> represent H, F, Cl, Br, nitro, (halogen-substituted) alkyl, aryl, aralkyl or OA (A represents H, alkyl, aryl, aralkyl or polyether); m and n are 1-4]. EXAMPLE:Tetra-1-phenyltetranaphthotetrazaporphyrinato copper complex-(1- phenyl-2,3-naphthalene-dicarboximide) (1/1). USE:An optical recording material having a characteristic light absorbance within a near infrared region of 750-850nm, which is soluble in variable solvents and stable to heat and light. PREPARATION:A mixture of a naphthalene derivative expressed by formula II with urea is subjected to cyclization reaction together with a metal (chloride), etc., in the presence of a catalytic amount of ammonium molybdate.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a novel tetraazaporphyrin compound having characteristic light absorption in the near-infrared region around 750 to 95 Q nm.

[Prior art and problems to be solved by the present invention] In recent years,
Various optical recording technologies using semiconductor laser light are under development by various companies around the world, and it is particularly desired to develop compounds that absorb light in the vicinity of 750 to 850 nm and are photoresponsive.

Conventionally, such compounds such as cyanine, merocyanine, squarylium base, pyrylium salt, triphenylmethane, and tetraazaporphyrin have been developed, but all of them are, for example, thermally unstable and soluble in solvents. It has various drawbacks such as poor properties, difficulty in handling, and decomposition by light, and has many problems for industrial use. Regarding tetraazaporphyrin compounds in particular, they are characterized by being stable against heat and light, but they have poor solubility in organic solvents, etc., and cannot be formed into thin films by solution coating. It was common to form thin films by vacuum evaporation.

[Means to solve the problem]

The inventors of the present invention conducted intensive studies to solve the problems of the above-mentioned conventional techniques, and found that the general formula (1) [wherein M is an atom of the LA group in the periodic table or an atom of the LA group or an atom of the LA group in the periodic table] group atoms or transition metal atoms, R1 and R
2 are the same or different, each independently a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, a nitro group, a linear or branched alkyl group, an aryl group that may be substituted with a halogen atom, an aralkyl group, a polyether group, or an OA group (wherein A represents a hydrogen atom, a linear or branched alkyl group, an aralkyl group, an aralkyl group, or a polyether group) m and n are Each independently represents the number of R1 and R2, and m and n each represent an integer of 1 to 4.] A tetraazaporphyrin compound represented by the general formula (2) [wherein Y and 2 are each independently 0 or N
H, R1, 几2. A compound to which one or two molecules of a naphthalene derivative represented by m and n have the same meanings as above] is soluble in various organic solvents, and is stable to heat and light, resulting in good processability. I found it to be excellent.

Next, definitions of various terms included within the scope of the present invention mentioned in the description of this specification and appropriate examples thereof will be explained below.

Examples of the la group atoms include hydrogen atom, lithium atom, sodium atom, and potassium atom.

Examples of the la group atoms include magnesium atoms, calcium atoms, and the like.

Examples of the la group atoms include aluminum atoms, indium atoms, and thallium atoms.

Examples of transition metals include titanium atoms, vanadium atoms, chromium atoms, manganese atoms, iron atoms, cobalt atoms,
Examples include nickel atom, copper atom, zinc atom, etc.

Examples of the alkyl group include methyl group, ethyl group, propyl group, butyl group, isobutyl group, 1-1-dimethylethyl group, pentyl group, isopentyl group, hexyl group, decanoyl group, octyl group, ethylhexyl group, and trifluoromethyl group. Examples include straight-chain or branched alkyl groups which may be substituted with halogen atoms such as groups. The preferred carbon number of the alkyl group is 01 to CIG.

Examples of the aryl group include phenyl group, ethylphenyl group, propylphenyl group, isopropylphenyl group,
Examples include butylphenyl group, isobutylphenyl group, 1-1-dimethylethylphenyl group, trifluoromethylphenyl group, methoxyphenyl group, ethoxyphenyl group, chlorophenyl group, and the like. The preferred number of carbon atoms in the aryl group is 06 to C+O.

Examples of the aralkyl group include phenylmethyl group, phenylethyl group, methylphenylmethyl group, ethylphenylmethyl group, and methoxyphenylmethyl group. The preferred number of carbon atoms in the aralkyl group is CF""C+0.

Examples of the tetraazaporphyrin compound in which one or two molecules of the naphthalene derivative represented by the general formula (2) are added to the tetraazaporphyrin compound represented by the general formula (1) include tetra-1-phenyltetranaphthotetraazaporphyrina Copper complex (1-phenyl-2,3
-naphthalene dicarboximide) 1 molecule addition compound, tetra-1-(1-1-dimethylethylphenyl)-tetra-7-(1-1-dimethylethyl)tetranaphthotetraazaporphyrinato copper complex (1-(1 -1-dimethylethylphenyl)-7-(1-1-dimethylethyl)
-2,3-naphthalene dicarboximide) 1 molecule addition compound, tetra-1-(trifluoromethylphenyl)
-Tetra-7-(trifluoromethyl)tetranaphthotetraazaporphyrinato copper complex (1-trifluoromethylphenyl-7-tetratrifluoromethyl-2.3-
naphthalene dicarboximide) 1 molecule addition compound, tetra-1-(dimethoxyphenyl)-octa-6,7
-(dimethoxy)tetranaphthotetraazaporphyrinato zinc complex (1-dimethoxyphenyl-6,7-simethoxy2,3-naphthalene dicarboximide) bimolecular addition compound, tetra-1-(dimethylphenyl)-octa-6, 7-(dimethoxy)tetranaphthotetraazaporphyrinato zinc complex (1-dimethylphenyl-6,7
-cymethoxy2.3-naphthalene dicarboximide) bimolecular addition compound, tetra-1-(trimethylphenyl)-tetra-7-(
phenylmethylphenyl) tetranaphthotetraazaporphyrinato zinc complex (1-trimethylphenyl-7-phenylmethylphenyl-2゜3-naphthalene dicarboximide) bimolecular addition compound, tetra-1-(bromophenyl)-tetra-7 -(Pentoxy)tetranaphthotetraazaporphyrinato copper complex (1-bromophenyl-7-pentoxy-2,3-naphthalene dicarboximide) one molecule addition compound, and the like.

A tetraazaporphyrin compound in which a naphthalene derivative represented by general formula (2) is added to a compound represented by general formula (1) can be produced as follows. A mixture of a naphthalene derivative and urea, represented by ■'*n2eY+ Z *m and n have the same meanings as above, is subjected to a ring-closing reaction together with a metal or a metal compound such as a metal chloride in the presence of a catalytic amount of ammonium molybdate. The reaction proceeds easily under heating.

The above tetraazaporphyrin compound with a naphthalene derivative added to it and the tetraazaporphyrin compound without a naphthalene derivative added thereto are soluble in a wide range of solvents, and examples include methanol, isopropyl alcohol, cellosolve, etc. alcoholic solvents, methylene chloride, chloroform,
It is soluble in halogenated hydrocarbon solvents such as trichlene, aromatic hydrocarbon solvents such as benzene, toluene, and xylene, and ether solvents such as ethyl ether and tetrahydrofuran.

Furthermore, since this compound is not only soluble in a wide range of solvents but also stable to light and heat, it is possible to obtain a highly pure compound by silica gel or alumina chromatography, if desired.

It has become possible to obtain a tetraazaporphyrin compound that is soluble in such a wide range of solvents and is stable to heat and light.

〔Example〕

EXAMPLES The present invention will be specifically described below with reference to Examples.

Example 1 2', ? ', 12', 17-tetraphenyltetra (blank below) naphtho (2,3,-b:2',3'-g:(',g'-
#: 2''', f'-q] Synthesis of one molecule addition compound of tetraazaporphyrinato copper complex (1-phenyl-2,3-naphthalene dicarboximide) Phenylpropiolic acid 10, O to acetic anhydride somg
f (68.4 mmol) was added and heated under reflux for 3 hours. The reaction solution was distilled off to a total volume of 25 ml. At this time, crystals began to precipitate. After the liquid was further cooled to about 5° C., the precipitated crystals were collected by filtration and dried under reduced pressure to obtain 8.91 1-phenyl-2,3-naphthalene dicarboxylic anhydride. Yield 94.8% (melting point 261 degrees).

The generated compound was used as it was in the next reaction.

8.0 g (29.2 mmol) of 1-phenyl-23-naphthalene dicarboxylic anhydride obtained by the above synthesis.
,urea! , '5 f (58.3 mmol), #1 chloride #40.7229 (7.3 mmol), and 0.1 g of ammonium molybdate were crushed and mixed in a mortar, heated while uniformly mixing, After heating to 260°C over 2 hours, the reaction was maintained at this temperature for 5 hours. After cooling the reaction mixture to room temperature, the solidified reaction mixture was ground in a mortar and purified by column chromatography (silica gel: benzene), and the desired fraction was concentrated to yield 2,7°12.17-tetraphenyl. Tetranaphtho [23-b:2', 3'-g:2.3-J:2',! '
-q) Dark green crystals of one molecule of tetraazaporphyrinato copper complex (1-phenyl-2,3-naphthalene dicarboximide) addition compound were obtained. Dry under reduced pressure to 0
．． I got 81. Yield 8.1% IR: (KB r ,
cm”) 3058.1779,1725,13711323.1
281,1118,1029゜900.756,702 Decomposition temperature: 440.9℃ Mass: 1352 (FAB) UV/VI 8/NI R; (Rioform, nm
) Clogε) 32 G (6,06), 709.5 (4,74).

798 (5,43) Example 2 2', 7', 12', 17'-tetra-(
4-trifluoromethylphenyl)-27,7,12,
17-Adler(trifluoromethyl)-tetranaphtho 1:2.3-b:2', 3'-g:2', 3'-7:2
,'y-q) tetraazaporphyrinato copper complex (1-
(4-trifluoromethylphenyl)-7-1-lifluoromethyl-2,3-naphthalene dicarboximide)
Synthesis of one molecule addition compound 4-trifluoromethylbenzaldehyde 136, 69
(0,785 mol), malonic acid 1614'I (15
7 mol), piperidi 716. s ml (0.1 symol) was heated and stirred in 400 mII of piperidine at 110° C. for 3 hours. 480 ml of concentrated hydrochloric acid was added under ice-cooling, and the precipitate was collected by filtration. After drying, it was recrystallized from 4000 ml of toluene to obtain 153.87y of 4-trifluoromethylcinnamic acid. Yield 90.7% IR(](, [3r, c
m) 1708.1640,1328,1188°1138.
1074,842 NMR (DM80-ds, δppm) 6.67 (
IH, d, J=16) 7, 5 8 - Otsu 96 (5H, m) 12.5
1(IH,br) Then 4-trifluoromethylcinnamic acid 152.8f (
0,707 mol) of carbon tetrachloride 800 m/! suspended in
45.7 ml (0,848 mol) of bromine was heated under reflux.
It took some time to drip. After the dropwise addition was completed, the mixture was further heated under reflux for 2 hours. Next, the solvent and excess bromine were distilled off under reduced pressure. 500ml of hexane left behind! was added to crystallize. The precipitated crystals were collected by filtration and then dried to obtain 259.1 g of 2,3-dibromo-3-(4-)lifluoromethylphenyl)propionic acid. Yield 91.5% Melting point
21G-213℃ 1 liter (KBr, cm) 1718.133B, 1180.1140゜1070.
85O NMR (DM80-ds, δppm) 5.37 (I
H, d, J=12) 5.68 (IH, d, J=12) Otsu 70-Otsu 9 f; (4H, m) 8.33 (IH, br s) 2.3-dibromo-3- 182.7 g (0,486 mol) of (4-)lifluoromethyl)propionic acid was suspended in 600 ml of a 25% potassium hydroxide-methanol solution, and methanol was distilled off at normal pressure on a water bath. The reaction was completed by adding 600 ml of methanol to the residue and distilling it off in the same manner three times.

After cooling with water, concentrated hydrochloric acid was added to the final reaction residue to adjust the pH to approximately 2, and the precipitated oil was extracted three times with 300 ml of chloroform. After drying the chloroform extract over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure. The obtained residue was recrystallized from 250 ml of carbon tetrachloride, and 53. II/trifluoromethylphenylpropiolic acid was obtained. Yield: 51. θ% Melting point 16G-181°C IR (KBr, cm-') 22411.1B98,1324,1140°1072
．． 856 NMR (DM80-ds, δppm) Otsu60-
Otsu 8G (4H, m) 8.85 (IH, br 5) (4-trifluoromethylphenyl)propiolic acid 5
0. Of (0,23S mol) in acetic anhydride 250 m
The mixture was heated under reflux for 3 hours. Next, add the reaction solution to a total volume of 100
It was concentrated to m#, and the precipitated crystals were collected by filtration. The filtered crystals were washed with 30 mA' glue globin and then dried.
45.5f(Dl-(4-trifluoromethylphenyl)-7-(trifluoromethyl)2.5-naphthalenedicarboxylic anhydride was obtained. Yield 95.2% Melting point 258-260°C IR (KBr , Cm) 1836.1776.1321.113G.

1065.901 NMR (CDOlg, δppm) Otsu 74-8.75 (7H, m) 9.05 (IH, δ) 1-(4-1 Lifluoromethylphenyl)-7-(Trifluoromethyl)2. 3-naphthalene dicarboxylic anhydride 20.429 (49.8 mmol), urea 8.59
F (110 mmol), 1.24 f of cuprous chloride, and 0.204 f of ammonium molybdate were ground and mixed in a mortar, heated while stirring uniformly, and heated to around 280°C over a period of 2 hours. This temperature was maintained for 2 hours. Next, the reaction mixture was cooled to room temperature, and the solidified reaction mixture was transferred to a mortar and ground. This reaction mixture was then purified by column chromatography (silica gel: benzene-hexane) and the desired fraction was concentrated to give 2,7,12°17'-tetra-
(4-trifluoromethylphenyl)-2',7",1
2',17'-tetra-(trifluoromethyl)-tetranaphtho (2,3-b: 2'.

3/-g: 2″, 3″-, ,2,3-q]tetraazaporphyrinato copper complex (1-(4-trifluoromethylphenyl)-7-1lifluoromethyl-2°3-naphthalenedi One molecule of the adduct (carboximide) was obtained.

Drying under reduced pressure yielded 0.6391/. Yield 2.5% IR (KBr, cm ) 17g2,1731,1618,1502°1360.
132G, 1288.1162°1108.1068.
1019.908° Melting point 300°C or higher UV/VIS/NIR (X til cellosolve, nm) (l
ogε) 254.5 (5,19), 415.0 (Sh).

422°0 (sh), 695.5 (4,67) 781,
0 (5,42) Example 3 2.7,12.17-tetra(4-(1,1-dimethylethylphenyl)-2', 7', 12', 17
Futetler (1,1-dimethylethyl)tetrana 7)
(2,3-b:2, 3'-g:2
'', 3''-z+2.

3-q] Tetraazaporphyrinato copper complex (1-(4-
(1,1-dimethylethyl)phenyl)-7-(1,1
-Dimethylethyl)2.3-naphthalene dicarboximide) Synthesis of one molecule addition compound 1-(4-(1,1-dimethylethyl)phenyl)-7
-(1,1-dimethylethyl)2,3 naphthalene dicarboxylic anhydride 24.00 f (li2.1 mmol),
urea 8.809 (147 mmol), ff1-copper chloride 1.54 g and ammonium molybdate 0.248
Mix 9 in a mortar and heat while stirring evenly.
It took some time to heat up to around 290°C. At this temperature 4
After reacting for an hour, the reaction mixture was cooled to room temperature, and the solidified reaction mixture was transferred to a mortar and ground. This reaction mixture was then purified by column chromatography (silica gel: benzene-hexane), and the desired fraction was concentrated to form dark green crystals.
Tetra(4-(1,1-dimethylethyl)phenyl)
-27,77,12', 177-tetra-(1,1-
dimethylethyl)tetranaphtho(2,3-b:2',3
'-g:2'',3''-1:2,3-q) Tetraazaporphyrinato copper complex (1-(4-(1,1-dimethylethyl)phenyl)7-(1,1-dimethylethyl )2.
3-naphthalene dicarboximide) 1 molecule adduct compound 0.30f was obtained. Yield 1.3% IR (KBr, cm ) 2960.2855, 2865, 1780°1728.
1372.127Q, 1118 Melting point 300℃ or higher UV/VIS/NIR (-Y-Tilcellosolve, nm)
(logε) 2 5 Otsu 5(6,13), 32
L, S (4,98).

709,5 (4,64), 798.5 (5,3
6) Reference Example Using the compounds obtained in Examples 1, 2, and 3, the solubility in the following solvents and stability against light and moist heat were measured. The measurement results are shown below.

(1) Compound obtained in Example 1: (Dissolved material) Toluene 15 w/v% Chloroform 15 w/v% Trichloride 1 Q w/v% (Stability against light) Glass plate by spin code method As a result of forming a thin film of the compound on the top and measuring the change in the film at 63°C under a light source with the same wavelength as sunlight using a spectrometer, the light absorption waveform after 1000 hours was the same as the light absorption waveform before light irradiation. No changes were observed in comparison. Maximum light absorption wavelength: 825 Gm (Stability of compound under high temperature and high humidity) A thin film of the compound is formed on a glass plate using the spin code method, and changes in the film are observed using a spectrometer at a temperature of 70°C and humidity of 90%. As a result of measurement using the same method, no change was observed in the light absorption waveform after 1000 hours compared to the light absorption waveform immediately after the thin film was formed. Maximum light absorption wavelength: 25 nm (2) Compound obtained in Example 2: (Solubility) Toluene l 5 w/v% <Chloroform 'l Q w/v% <Trichlene
”l Q w/v%〈ether l Q w/
v%〈 Cellosolve 5 w/v%〈 (Stability against light) As a result of measurement under the same conditions as the measurement of the stability against light of the compound obtained in Example 1, the light absorption waveform after 1000 hours was the same as that before light irradiation. No change was observed compared to the optical absorption waveform of .

Maximum light absorption wavelength = 800 m (Stability of compound under high temperature and high humidity) As a result of measurement under the same conditions as the stability measurement under high temperature and high humidity of the compound obtained in Example 1, the light absorption after 1000 hours was No change was observed in the waveform compared to the light absorption waveform immediately after the thin film was formed.

Maximum light absorption wavelength: 800 nm (3) Compound obtained in Example 3 (solubility) Toluene 2Q w/v% Chloroform 3 Q w/v%〈Trichlene'l 5 w/v%〈Ether 1 Q w/v % Cellosolve l Q w/v%〈 (Stability to light) As a result of measurement under the same conditions as the measurement of the stability to light of the compound obtained in Example 1, the light absorption waveform after 1000 hours of light irradiation was No change was observed compared to the light absorption waveform before irradiation. Optical absorption maximum wavelength: 2 15 nm Stability of compound under high temperature and high humidity As a result of measurement under the same conditions as the stability measurement under high temperature and high humidity of the compound obtained in Example 1, the light absorption waveform after 1000 hours was that of a thin film. No change was observed compared to the optical absorption waveform immediately after formation. Maximum light absorption wavelength = 15 nm [Effects of the invention] According to the present invention, a novel tetraaza that has characteristic light absorption properties in the near-infrared region and is excellent in various aspects such as solubility, photostability, and thermal stability. Porphyrin compounds are provided.

Claims (1)

[Claims] 1) General formula (1) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (1) [In the formula, M is an atom of group Ia or II in the periodic table.
Represents a group a atom, a group IIIa atom, or a transition metal atom, and R^1 and R^2 are the same or different and each independently represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, a nitro group, a halogen A straight-chain or branched alkyl group, aryl group, aralkyl group, polyether group, or OA group that may be substituted with an atom (wherein A is a hydrogen atom, a straight-chain or branched alkyl group) group, aryl group, aralkyl group or polyether group), m
and n each independently represent the number of R^1 and R^2, m and n each represent an integer from 1 to 4]
The tetraazaporphyrin compound represented by the general formula (2) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(2) [In the formula, Y and Z each independently represent O or NH, R^1, R^ 2, m and n have the same meanings as above] A compound to which one or two molecules of a naphthalene derivative are added. 2) The compound according to claim 1, wherein M is copper or zinc.