JPH02232267A - Tetrapyrazinoporphyrazine compound - Google Patents

Abstract

NEW MATERIAL:A compd. of formula I [wherein R1-8 are each H, a phenyl or a furyl, provided that not all of them are H; M is H (or 2H), a metal, a metal (hydr)oxide, an acyl-, an alkoxy- or a siloxy-metal or a metal halide]. EXAMPLE:A compd. of formula II. USE:An optical recording medium, a photosensitive material for electrophotography and laser printing, an oxidation-reduction catalyst and a freshness retainer for flowers, cut flowers and foods. PREPARATION:2,3-Dicyanopyrazine of formula III (wherein Rx and Ry are each R1-8) or 1,3-diimino-2H-pyrrolo[3,4-b]-pyrazine which is a reation product of NH3 therewith is heated with a metal (oxide), a metal salt, a metal halide or nothing [wherein M is H (or 2H)] in an inert solvent with a high b.p. (e.g. dichlorobenzene).

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to novel tetravirazinovolfilazine compounds. Since the derivatives of the present invention are stable and have strong absorption of near-infrared rays, they can be used as optical recording media, photosensitive materials for electrophotography, laser printers, redox catalysts, freshness-preserving agents for cut flowers, foods, etc. It is possible. (Prior art) Cyanine dyes, squarylium dyes, naphthoquinone dyes, and phthalocyanine dyes, which are materials that absorb near-infrared light or visible light, have been used in optical recording media, electrophotography,
Phthalocyanine dyes are expected to be applied to laser printers, etc., but phthalocyanine dyes have the best durability and near-infrared to visible light absorption properties, and have been studied in various ways. Particularly in recent years, phthalocyanine dyes that are highly sensitive to laser light are expected to be used as optical recording materials and light-sensitive materials for laser printers, and various new tank structures have been proposed. To give an example of these, for example, Journal or General Chemis introduces a substituent into the benzene ring of phthalocyanine.
try, USSR. Ai. 2075 (1976) (
Amino group-introduced type): Textile and Polymer Materials Research Institute Research Presentation Materials, 1985, page 167 (Octaalkoxy Go-introduced type): JP-A-63-170462 (Amino group-introduced type)
; JP-A-60-209583, JP-A-63-27076
5, (thioether introduction type); Japanese Patent Publication No. 59-1311 (
(ether or thioether introduced type). Also 780~
In order to have a strong absorption at 830n, an aromatic ring is further condensed to the benzene ring of the captic cyanine to reduce the transition energy of the conjugated π electron.For example, in the following formula [■] Y: Y:, Y is a naphculene ring. Japanese Patent Application Publication No. 61-2588
6, JP-A-61-177288, JP-A-61-2684
87, JP-A-62-56191, JP-A-62-1227
88, JP-A-62-10093, JP-A-63-2755
There are naphthalocyanine compounds such as No. 84, and tetraphenanthroborphyrazine compounds such as JP-A No. 63-87282, in which Y is a phenanthro group. These attempts have mainly focused on practical semiconductor laser sensitivity, but this alone is still not sufficient for practical use. For example, in addition to the above two points, optical recording materials must have a high reflectance, a not very high melting point or decomposition point, a high threshold value, a low thermal conductivity, light, It is necessary to have high resistance to oxygen, to withstand regeneration more than 10" times, and for laser printers, it must have an appropriate ionization potential to obtain high charge injection efficiency in combination with a charge transport material. , small dark decay to obtain a highly sensitive latent image, laser light,
Performance such as high durability against oxygen is required. [Problems to be Solved by the Invention] The present invention has been made in view of the above-mentioned circumstances, and its purpose is to replace the benzene ring, which is the basic structure of the lid cyanine lamp, with a virazine ring and create tetravirazinovolfilazine. Another object of the present invention is to provide novel tetravirazinovolphyrazine compounds in which the above-mentioned various properties related to the basic structure of the molecule are modified by introducing substituents into them.
A compound having a structure similar to the tetrapyrazinovolphyrazine compound according to the present invention is represented by the following formula (Iff).
1 = R @ − H (Gal'pern, l
i. G. :Luk'yaneLs. Fi. Eight. ，
Zh. Obshch Khim. Vof.
39 No. 11. 2536-41. (196
9th year) BIzv. Akad. Nauk SSSR, Se
r. κlm. ．． LiL1.1976) R+””R-CH* (Japanese Patent Application Laid-open No. 61-291187) R. -n
x ”Calls (56th Annual Meeting of the Chemical Society of Japan (1988
) Lecture proceedings 2X. II [! 35) R+”
” R t -CONIlt (Sυ-1132300
(1984))R. Either one of Rt is 8u1 and the other is ]I (Gal'perr+, M.G.:
Luk'yanets. E. ^,, Whim. G
eterotslkl. Soedln. ．． (6),
85B-9. (1972): IZV, ^kad.
Nauk SSSR. Ser. K4g+. ．． , [JJ
, 1976], but these compounds are still insufficient in terms of organic solubility, semiconductor laser sensitivity, and other properties. 1) [In the formula, R + "" Re are the same or different and represent hydrogen 1, a phenyl group, or a furyl group. However, R + "" R
Not all s are hydrogen. M represents hydrogen (2H), metal, metal oxide, metal hydroxide, acyl metal, alkoxy metal, siloxy metal, or metal halide. ) is a tetrapyrazinoborofuirazine compound. M in formula (1) is hydrogen (2H), a metal, a metal oxide, a metal hydroxide, an acyl metal, an alkoxy metal, a siloxy metal, or a metal halide, such as M g SA
I C I, S i C I x S l (O
H) fi, Si (COCH3)! Si(OCR2
)* Si (OSi (CH3)!)z
Ca, TiO, VO, C r SM n s F e
．． ．． Co, Ni, Cu, ZnSGa, Ge, ZrO
, NbSMo, Ru, PdS InCI, InBr, S
n, SnCIs, SnBrx Snl*Ta
Indicates SPb, Bi (lanthanide), etc. The tetrapyrazinoborofuirazine compound of the present invention is Fr
ank II. Moser. ArLhur L.
by Thomas, r Phthalocyani
nas J (19B3 CRC PR [!
55) iJournal of Chemical
Society+ 911 (1937);
rnafofthe＾*erican'Che placedica
lSocjety+85.668 (1963); Zh
urnal Obshchef κhrail, 3
9.2536 (1969); Journal o
r Heferocyclic Chemistry
2,3-dicyanovirazine, which may have a substituent represented by R I "? R s, or its NH. [M : hydrogen (2H)), if necessary, in a high boiling point inert solvent such as quinoline, trichlorobenzene, dichlorobenzene, chlornaphthalene, etc.
In addition to being produced by heating to °C,! -dimethylamino-2-ethanol, l-dimethylamino-2-
It can also be easily produced by blowing ammonia gas into an alcohol such as propanol under stirring and reflux. Examples of metals, metal oxides, metal salts, and metal halides include M g , M g C +! , Mg
O , A I C I s S I C I =
T I C I s VC I s C r
(O A c ) * M n O z , M n
, F e C I s C o C I! N
i C I t N i, CuC I, CICIt
, ZnCli %GaCIt, G e C I a
Z r C I s N b-halide, Mo
, R u C I s P d C I * r
n C I z , I n B r s, Sn1Sn
CIg SnBr* Snug Ta-halide, PbO lanthanide halide, lanthanide acete
One example is one. Optionally substituted 2,3-dicyanovirazine (V), which is one of the synthetic raw materials of the present invention
is synthesized by reacting DAMN and diketone (IV) in water, alcohol, or organic acid. Here, Rx and Ry are -R+ and Rt, Rs and R4R, and R&
Rq and R. , and R+-Ri has the same meaning as above. Diketone (IV) is OrganicRea
cLtons s 4, 2.6 9 (1 9 4 9
), OrganicSynthesis Coll.
νol. 5, 111, etc., using a conventionally known method. [Example] Next, the present invention will be further explained with reference to Examples. Example l Synthesis of 2, 3, 9, 10S 16, 17, 23, 24-octaphenyltetrapyrazinovolphyrazine [■]
0 4 1-dimethylamino-2-probanol 7d was placed in a three-necked Hertzian flask, and ammonia gas was introduced. After heating to about 100°C, dicyanophenylhydrazine ('Vr) 1. 0 g (3.5 +w
mol) and stirred and refluxed for 7 hours. After cooling, it was filtered, washed with methanol and acetone, and soluble impurities were removed by Soxhlet extraction with methanol and acetone. Furthermore, the target product [■] was extracted with chloroform, the solvent was distilled off using an evaporator, and the product was further washed with acetone. yield. ．． 22g (yield 22%). IR: 3300.1510,760.70
0cm −'υV-VIS: 639,669
na (solvent, methylene chloride FAB-MS (a+/z): 1131 (P+1),
(Calculated value 1131.22) Example 2 2, 3, 9, IO, l6, 17, 23, 24 one octa (
Synthesis of 2-furyl) tetravirazinovolfilazine ([X)
0d 1-dimethylamino-2 in 3 Rohertz flasks
-Probanol 5id was added and ammonia gas was introduced. After heating to about 100°C, dicyano(2-furyl)vilazine [■]1. Og (3.8su+ol) was added, and the mixture was stirred and refluxed for 8 hours. After cooling, filter methanol,
After washing with acetone, soluble impurities were removed by Soxhlet extraction with methanol, acetone, and chloroform. Furthermore, the target product ([X) was extracted with dichloromethane, the solvent was distilled off using an evaporator, and the extract was further washed with acetone. Yield: 0.16g (yield: 16%). I.R.
: 3300.1570, 1540.750c
m-'IJV-VIS: 666.690nm
(Solvent, methylene chloride FAR-MS (m/z): 1051 (P÷1), (
Calculated value: 1050.93) [Effect of the invention] The tetravirazinovolphyra compound of the present invention can be easily produced by a simple operation as described above, and can effectively emit near-infrared light or visible light. optical recording medium, for absorbing
It can be effectively used as a photosensitive material for electrophotography, laser printers, redox catalysts, flowers, cut flowers, and food freshness preservation agents. Applicant (430) Nippon Soda Co., Ltd.

Claims (1)

[Claims] (1) General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [I] [In the formula, R_1 to R_8 are the same or different and represent hydrogen, phenyl group, or furyl group, provided that R_1 to R_6 are It's not all hydrogen. M is hydrogen (2H), metal, metal oxide, metal hydroxide,
Indicates acyl metal, alkoxy metal, siloxy metal or metal halide. ] A tetrapyrazinoporphyrazine compound represented by