JPH0253864A - Porphyrazine compound - Google Patents

Abstract

NEW MATERIAL:A tetranaphtho [2,3-b:2',3'-g:2'',3''-:1:2''',3''' -q]porphyrazine compound [M is 2H, elements of groups Ia, IIa, IIIa, IIIb, IVb, Vb, VIb or VII; Y1 and Y2 are halogen, OH or O; at least one of R1-R8 is aminoalkoxy shown by formula II (Q is 1-10C alkyl; R9 and R10 are H, 1-10C alkyl, etc.) or is 1-18C alkyl-containing alkoxy when residual group exists; X is H, halogen or nitro; n is 0-4]. EXAMPLE:21H,23H-2<1>,2<6>,7<1>,7<6>,12<1>,12<6>,-17<1>,17<6>-octakis-( diethylaminoethoxy)- tetranaphto[2,3-b: 2',3'-g:2'',3''-1:-2''',3'''-q]porphyrazine. USE:A dyestuff soluble in organic solvent. PREPARATION:A naphthalene compound shown by formula III (R11 and R12 are 1-18C alkyl-containing alkoxy) is heated in amino alcohol shown by formula IV in the presence of an alcoholate shown by the formula ZOR11 (Z is Na or K) and subjected to ring closure reaction.

Description

Detailed Description of the Invention [Industrial Application Field] The present invention is directed to novel tetranaphtho 1-2 having characteristic absorption in the near-infrared region around 750 nm to 850 nm.
．． 3-1): 2', 3'-F: 2'', 3
″-1:2′″3′″-q] relates to a porphyrazine compound and a method for producing the same.

[Prior art and problems to be solved by the present invention] In recent years,
Various technologies using semiconductor laser light have been developed, and 75
It is desired to develop a compound that has absorption in the vicinity of 0 nm-85Q nm and has a photoresponse.

In the conventional technology, such compounds include cyanine-based, merocyanine-based, squarylium base, pyrylium salt-based, anthraquinone-based, triphenylmethane-based,
Examples include porphyrazine series expressed as phthalocyanine and naphthalocyanine. All of the above-mentioned compounds have various drawbacks, and many problems arise when they are used industrially. Especially tetranaphtho [2,3-b:2'3
'y:2'', 3''-1:2'/, 3''/-q] Regarding porphyrazine compounds (hereinafter sometimes abbreviated as naphthalocyanine), the solubility in organic solvents etc. It was difficult to form thin films by solution coating, and thin films were generally formed by vacuum evaporation. In addition, naphthalocyanine compounds that are soluble in organic solvents have been developed in recent years, but there are still few that are soluble in solvents that do not attack the surface of plastic substrates, and there are no compounds that allow dye solutions to be applied directly to plastic substrates.

[Means to solve the problem]

The present inventors conducted intensive studies to solve the problems of the above-mentioned conventional technology, and found that a specific naphthalocyanine compound represented by the general formula (1) is soluble in various organic solvents. As a result, it was found that the processability was excellent.

(X)n [In the formula, M is 2 hydrogen atoms or Ia+, IIa+
ma+mbl ]Vt) + vb+ Wb
or ■ represents an element of the b group, iY, and ¥2 each independently represent a halogen, hydroxyl group, or oxygen, and ++R2+ skin, ■. , skin 5. And. , ■, 7 and 8, at least ~C+8 straight or branched alkyl group i R9 and 几 are each independently hydrogen, 01
~C1o alkyl or cycloalkyl group, C-
C,o alkenyl or cycloalkenyl group, 0
1-CIO allyl or aralkyl group, or skin, and.

is bonded through a carbon atom or a petro atom to form a 3- to 7-membered heterocycle with the nitrogen atom in the formula)
The remaining groups, if any, represent an alkoxy group having a linear or branched alkyl group of 01 to C18.

X represents hydrogen, halogen or nitro group, n is 0-
] In addition, in formula (I), the substituent represented by Q is, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, 1,1-dimethylethyl, pentyl. , impentyl, hexyl, decanoyl and the like.

R9 and Rin. Examples of the 01-C1o alkyl or cycloalkyl group represented by include methyl, ethyl, n-propyl, isopropyl, n-butyl, inbutyl, 1,1-dimethylethyl, pentyl, impentyl, hexyl, decanoyl, cyclopropyl, cyclobutyl, Examples include cyclopentyl, cyclooctyl, etc., and 0
Examples of the 1-C1o alkenyl group include propenyl, butenyl, octenyl, pentenyl, cyclopentenyl, cyclobutenyl, cyclooctenyl, cyclohexenyl, etc., and examples of the 01-C1o allyl or aralkyl group include phenyl, methylphenyl, ethylphenyl. , propylphenyl, isofuropylphenyl, butylphenyl, imbutylphenyl,
1,1-dimethylethylphenyl, trifluoromethyl, trimethylsilylphenyl, methoxyphenyl, ethoxyphenyl, chlorophenyl, bromophenyl, phenylmethyl, phenylethyl, methylphenylmethyl,
Examples include ethylphenylmethyl and methoxyphenylethyl. In addition, ■, and]11o are bonded via a carbon atom or a heteroatom, and together with the nitrogen atom in general formula (1), 3-
Examples of those forming a 7-membered heterocycle include 1-morpholino, 1-thiomorpholino, 1-piperidino, and the like.

Examples of the naphthalocyanine compound represented by the general formula (1) include octa(diethylaminoethoxy)naphthalocyanine, octa(diethylaminoethoxy)naphthalocyanine cobalt complex, octa(diethylaminoethoxy)naphthalocyanine copper complex, octa(diethylaminoethoxy)naphthalocyanine Phthalocyanine nickel complex, octa(
(diethylaminoethoxy) naphthalocyanine aluminum complex, tetra(diethylaminoethoxy)-tetra(
methoxy) naphthalocyanine, tetra(diethylaminoethoxy)-tetra(pentoxy)-naphthalocyanine, tetra(dibenzylaminoethoxy)
-Tetra(pentoxy)naphthalocyanine, tetra(dicyclohexylaminoethoxy)-tetra(pentoxy)naphthalocyanine, tetra(dicyclohexenylaminoethoxy)-tetra(pentoxy)tetranaphthonaphthalocyanine, tetra(1-morpholinoethoxy)- Examples include tetra(pentoxy)tetranaphthonaphthalocyanine, tetra(1-piperidinoethoxy)-tetra(pentoxy)tetranaphthonaphthalocyanine, and the like.

Compound (1) can be produced as follows.

That is, the following formula [where KN and "+2 are each independently 01 to C
AQ+ having 18 straight or branched chain alkyl
J and R4° are the same meanings as above)] and in the amino alcohol represented by the table (■) (wherein Q, ■. and 1° are the same meanings as above), the formula Z OR+ + [wherein, "H
is a straight chain or branched chain of C1 to C18, and R4゜ is the same as above); Z represents sodium or potassium]
Tetranaphtho (2,3-6: 2', 3
'-7=2//, 3//1: 2 ///, 3
'''Q:) Polyphyllazine (I') (Formula (I).

M=2H] is generated.

The reaction proceeds easily under heating.

The generated compound (I') may be selected from the periodic table Ia+ la+ ma, mb, IVI other than hydrogen, if desired.
)l Vb+ Vlb or ■b elements, such as lithium, sodium, potassium, rubidium, cesium, manesium, calcium, strontium, barium, yttrium, lanthanum, titanium, zirconium, vanadium, niobium tantalum, chromium, molybdenum, tungsten, manganese, etc. When reacted with an inorganic acid salt such as a metal halide compound or an organic acid salt such as an acetate in a solvent, the above-mentioned elements replace hydrogen and are introduced into the compound to form a complex compound. The metal salt may be a complex salt,
Further, a metal such as sodium or an organometallic compound may be used instead of the salt. The solvent for this reaction is determined by considering the solubility of compound (1'), the metal or metal compound to be reacted with it, and the complex compound formed, but there are many types of compound (I') and complex compounds. For example, 01-C4 alcohol; halogenated hydrocarbons such as chloroform and methylene chloride;
One can choose from a wide range of solvents including hydrocarbons such as hexane, benzene, toluene, ethers such as isopropyl ether, dioxane, pyridine, amines such as triethylamine.

[Action of the invention]

The above naphthalocyanine compounds are soluble in most solvents other than water, and to give an example, methanol,
Alcohol solvents such as ethanol, Improvyl alcohol, n-butanol, halogen solvents such as methylene chloride, chloroform, carbon tetrachloride, trichlene, aromatic solvents such as benzene, toluene, xylene, hexane,
It is soluble in hydrocarbon solvents such as heptane, ether solvents such as ethyl ether, isopropyl ether, and dioxane, and amine solvents such as pyridine and triethylamine.

The present invention is the first to demonstrate naphthalocyanine compounds that are soluble in such a wide range of solvents.

〔Example〕

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

Example 1 21H, 23H-2'267'7612'12
6.17. 17-octakis-(diethylaminoethoxy)-tetranaphtho(2,3-1): 2', 3
'-g: 2'', 3''-1: 2''', 3''
-q] Synthesis of porphyrazine 1,4 dimethoxy-2,3-dicarbonitrile naphthalene 1001 was added to a radium 2-diethylaminoethoxide solution prepared from 120 mJ of 2-diethylamine ethanol and 331 g of metallic sodium at an internal temperature of 95°C. 2
After heating and stirring for a certain period of time, the reaction is completed.

2-diethylamine ethanol was distilled off from the reaction solution under reduced pressure, and 100 ml of acetic acid was added to the residue, followed by stirring at room temperature for 30 minutes.

After acetic acid was distilled off from the reaction solution under reduced pressure, 200 ml of water was added to make an aqueous solution. After washing this with 100 ml of chloroform three times, the liquid was adjusted to pH around 8 with concentrated aqueous ammonia, and an oily substance was separated. This is ether 100 go 3
Extract in times. After drying the ether solution over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure. The obtained residue was purified by column chromatography (neutral alumina activity l: methylene chloride).
(methanol) and concentrate the desired fraction to obtain blackish brown crystals. Pour the obtained crystals into 50 m of water.
After suspending in 1), adjust the liquid level to around I)H4 with concentrated hydrochloric acid. After removing the suspicious substance from the furnace, cool the furnace liquid to 5 degrees, and gradually add concentrated ammonia water while stirring to adjust the liquid property to approximately d. When the mixture is stirred for 2 hours at a temperature of 30°C, crystals will precipitate.

The precipitated crystals are taken to the bottom of the furnace and thoroughly washed with water so that no basicity remains.

Drying under reduced pressure gives dark brown crystals 2.2y.

Yield 128% IR; (KBr, cm) 3298, 3064.29G8, 29322800.
1581, 1458, 12481095, 1047.
1023. 768HMR, (CI)C13, δ) 8.9-8.8 (8H, m), 7.72-7.62
(8Hm), 5.16-5.02 (161(t).

3.4-3.2 5 (16H,t), 2.
6 4-2.43 (32H, Q) 1.0-0.86 (3
(isopropyl alcohol, nm) (logε) 228 (5, OL 225.5 (4,9).

325.5 (4,8L 756 (4,6L853.5)
(5,3).

Example 2 2', 26.7'', 76.12', 126.17'17
6-octakis-(2-diethylaminoethoxy)-tetranaphtho(2,3-b:2', 3'g:2'' 3
″-1:2″/ 3#-q) Synthesis of porphyrazinato cobalt complex 21H, 23H-2, 2, 7, 7, 12″12617′
176-octakis-(2-diethylaminoethoxy)-tetranaphthoC2,3-b: 2'3'-9
: 2"3"-1: 2"', 3"'-CI) Dissolve 1.5 fl of porphyrazine in 20 ml of chloroform.

To this chloroporum solution, 1.59 cobalt acetate tetrahydrate dissolved in 15 vtl of methanol was added under heating to reflux.
Add it dropwise for 0 minutes. After the dropwise addition is completed, the reaction is completed by heating and stirring for 3 hours. After the reaction is completed, the solvent is distilled off under reduced pressure, and the resulting residue is purified by column chromatography (neutral alumina activity I: chloroform-methanol). The desired fractions were collected and the solvent was distilled off under reduced pressure to obtain 1.09 black-rimmed crystals.

Yield 644% IR; (Neato+) 297G, 2930, 2800, 1580° 1458,
1353. 1230. 1080°1013, 9
33. 762. 743UV/VIS/NIR; (
Isopropyl 7 /l/ :l-l, nm ) (lo
gε=) 224.5 (5,0), 323 (4,9).

718.5 (4,5L) 808.5 (5,2) Example 3 Using the compound of Example 1, the solubility in the following solvents was measured.

Solvent name Solubility (w/v%) Methanol 50> Ethanol 40> Improvyl alcohol 20> Methylene chloride 20> Chloroform 30> Carbon tetrachloride 20> Ethyl ether 10> Pyridine 50> Triethylamine 50> [Effects of the invention] According to the present invention Now, porphyrazine (cyanine) compounds, which were previously thought to be difficult to tolerate, have been provided with compounds that are soluble in a wide range of solvents, and a wide range of applications have become possible.

Patent applicant: Hamari Pharmaceutical Co., Ltd. (and one other person) Representative: Patent attorney Takashi Takeuchi "5゛"'.

Claims (1)

[Scope of Claims] 1 The following formula [wherein M is two hydrogen atoms or Ia, IIa, IIIa,
Represents an element of group IIIb, IVb, Vb, VIb or VIIb; Y_1 and Y_2 each independently represents a halogen, hydroxy group or oxygen; R_1, R_2, R_
3. At least one of R_4, R_5, R_6, R_7 and R_8 has a formula ▲ has a mathematical formula, chemical formula, table, etc. ▼ (wherein, Q is a straight or branched chain alkyl group of C_1 to C_1_0; R_9 and R_1_0 each independently hydrogen, C_1-C_1_0 alkyl or cycloalkyl group, C_1-C_1_0 alkenyl or cycloalkenyl group, C_1-C_1_0 allyl or aralkyl group, or R_9 and R_1_0 are bonded through a carbon atom or a heteroatom, and indicates an aminoalkoxy group represented by (indicating that it forms a 3- to 7-membered heterocycle with a nitrogen atom), and if there are any remaining groups, C_1 to C_1
Tetranaphtho[2,3-b:2' , 3′-g:2″, 3″-:1:2
′″, 3′″-q] porphyrazine compound. 2 The following formula ▲ Numerical formula, chemical formula, table, etc. ▼ [In the formula, R_1_1 and R_1_2 are each independently an alkoxy group having a straight or branched chain alkyl of C_1 to C_1_8, or the formula ▲ Numerical formula, chemical formula, table, etc. The naphthalene compound represented by ▼ (in the formula, Q, R_9 and R_1_0 have the same meanings as above) is expressed by the formula ▲ mathematical formula, chemical formula,
There are tables, etc. ▼ (In the formula, Q, R_9 and R_1_0
is the same meaning as above), in the amino alcohol represented by the formula ZOR_1_1 [wherein R_1_1 is C_1 to C_1_
8 straight or branched alkyl group or an alcoholate represented by the formula ▲ Numerical formula, chemical formula, table, etc. ▼ (wherein Q, R_9 and R_1_0 have the same meanings as above); Z represents sodium or potassium] Tetranaphtho [2, 3-b: 2', 3'-g: 2'', 3''-1
:2''', 3'''-q] polyphyllazine compound according to claim 1, wherein the polyphyllazine compound is optionally reacted with a metal, a metal salt of an inorganic or organic acid, or an organometallic compound. -b:2', 3'-g:2''
, 3″-1:2′″, 3′″-q] Method for producing porphyrazine metal complex.