JPH02232268A - Substituted tetrapyrazinoporphyrazine compound - Google Patents

Abstract

NEW MATERIAL:A compd. of formula I [wherein R1-8 are each H, or each pair of R1 and R2, R3 and R4, R5 and R6, or R7 and R8 forms together with two adjacent C atoms of pyrazine a (substd) 6C or larger ring (O-contg.), 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 and R2, R3 and R4, R5 and R6 or R7 and R8) or 1,3-diimino-2H-pyrrolo[3,4-b]- pyrazine which is a reaction 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 tetrapyrazinovolfirazine compounds. The derivatives of the present invention are stable, have strong near-infrared absorption, and have high solubility in general organic solvents, so they can be used as optical recording media, electrophotography, photosensitive materials for laser printers, redox catalysts, and flowers. It can be used as a freshness-preserving agent for boats, cut flowers, and food. [Prior art] Conventionally, cyanine dyes, squarylium dyes, naphthoquinone dyes, and futacyanine dyes, which are materials that absorb near-infrared light or visible light, have been used in optical recording media, electrophotography,
Although it is expected to be applied to laser printers, etc., cyanine dyes have the best durability and near-infrared to visible light absorption properties, and have been studied in various ways. Particularly in recent years, cap cyanine dyes that are highly sensitive to laser light have been sought after as optical recording materials and light-sensitive materials for laser printers, and various new structures have been proposed. An example of such a product is one in which a substituent is introduced into the benzene ring of futacyanine to improve solvent solubility and/or to have strong absorption in the 780 to 830 nm range.
General ChemjsLry, USSR
, ■． 2075 (1976) (amino group introduced type):
Textile and Polymer Materials Research Institute Research Presentation Materials 16, 1985
Page 7 (octaalkoxy group introduced type); JP-A-63-
17046'2 (amino group introduced type); JP-A-60-20
9583, JP-A No. 63-270765, (thioether introduction type): JP-A No. 59-. 1311 (ether or thioether introduced type). In addition, in order to have strong absorption at 780 to 830n+m, an aromatic ring is further condensed to the benzene ring of the phthalocyanine to reduce the transition energy of the conjugated π electron.For example, in the following formula (n) Y, Y is a naphthalene ring. Japanese Unexamined Patent Publication No. 61-25 8
8 6, JP-A-61-177288, JP-A-61-2
68487, JP-A-62-56191, JP-A-62-1
22788, JP-A-62-10093, JP-A-63-2
There are naphthalocyanine compounds such as No. 75584, and tetraphenanto-volufirazine compounds such as JP-A-63-87282, in which Y is a phenant group. These attempts have developed practical semiconductor laser-sensitive dyes that are solvent-soluble and/or 780-830 nm.
This work has mainly focused on two points: providing strong absorption to the surface of the material, but this alone cannot be said to be sufficient for practical use. For example, in optical recording materials,
In addition to the above two points, the reflectance is high, the melting point or decomposition point is not very high, their threshold is high, the thermal conductivity is low, and the resistance to light and oxygen is high.
It is necessary to withstand regeneration over 1Oh 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, and to obtain a highly sensitive latent image. Therefore, performance such as low decay and high durability against laser light and oxygen is required. [Problem to be solved by the invention] The present invention was made in view of the above circumstances, The purpose of this is to replace the benzene ring, which is the basic structure of futa-cyanines, with a pyrazine ring to form tetravirazinovolphyrazine, and to introduce substituents into these to improve the solubility in organic solvents and improve the basic structure of the molecule. The object of the present invention is to provide novel tetravirazinovolfirazine derivatives with modified various properties. A compound having a similar structure to the tetravirazinovolfilazine derivative according to the present invention is represented by the following formula (I[[) in which R+
-R*-Summer I (Gal'pern, M.G.:
k'yanets. E. Eight. , Zh. Ob
shch His. Vol. 39 No. 1
1. 2536-4L (1969)] R. -R. −
CH. (Unexamined Japanese Patent Publication No. 61-291187) R, -R yaw CJ
s (Chemical Society of Japan 56th Annual Meeting (1988) Lecture Proceedings 2
Xi[E35) R1-Rz-CONHz (SU-11.32
300 (1.984 years)) R + R t, one of which is t-Bu and the other is H (Gal'pern,
M. G. : Luk'yanets, E.A. ，
Khi*. Getsrotsikl. Soedln.
, (6), 858-9, (1972); lz
v. ^kad. Nauk SSSR, Ser. κhim
．． ．． Although there are compounds for each of the following (Yu 973, 1.976), these are still insufficient in solubility in organic solvents, sensitivity to semiconductor lasers, and other aspects. [Means for Solving the Problems] The present invention solves the problems according to the general formula (1) (wherein R1 to R@ contain hydrogen or two adjacent carbon atoms of pyrazine, and R1, R z R *, and R4R
, and R. - or R, and R. together form a ring having 6 or more carbon atoms. This ring may contain oxygen in the middle or may be ffla. However, R r −
Not all Rs 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 CT) is hydrogen (2H), metal, metal oxide,
metal hydroxides, acyl metals, alkoxy metals, siloxy metals or metal halides, such as MgSAIC
I, SiCIg , $1 (OH)Si(COCIHs
冫 x SI (OCHx
) zSi(OSrCCH3)s)tCa,TI
O, VO. ．． Cr, MnSFe%Co, NJ, Cu, Z
n, Ga, GeSZrOSNb. ．． Mo, RuSPdS
InCI% InBr, gn, SnCI,, SnBr
z Snug TaSPb, Bk (Rankini l''), etc. The tetraborphyrazine neck compound of the present invention is Frank
If. Moser, 8thur L. Thoma
Author: Phthalocyanines J.C.
19B3 CRC PRESS＞:JournaI
or CheIIIical Society+
911 (1937); Journal or the
Amertcan Chemical Soclet
y+85,668 (1963); Ztiurna [
Order Obschet Khim. 39.2536 (1
969); Journal or Heferology
cllc Chamlstry+1403 (1970)
The above R
,~R. The position indicated by ? 2,3-dicyanovirazine having AM or its reaction product with NH,
3-diimino-2H-virolo[3,4-b]virazine derivative and metal, metal oxide, metal salt, metal halide, or without using [M: hydrogen (2H)]L, if necessary, quinoline , trichlorobenzene, dichlorobenzene,
100-2 in a high-boiling inert solvent such as chlornaphthalene.
In addition to being produced by heating to 50°C, 1,8-diazabicyclo(
It can also be easily produced by stirring and refluxing in the presence of 5,4,O) undecene-7 (DBU).
Examples of metals, metal oxides, metal salts, and metal halides include Mg. ．． MgC1t, MgO, A I C I
s S i C I - T I C I 4
V C I z C r (O A c ) z
M nOt Mn, FeCIz CoCIz
NiCINj, Cu. CI, CICIi, ZnC
I, GaCIt, GeCIa ZrC1a Nb
- Halide, MoSRuCIz PdCIx
InCIs InBrs SnSSnCIt
Examples include SnBrSnlz Ta-halide, PbO lanthanide halide, and lanthanide acetate. 5,6-monosubstituted 2,3- which is one of the synthetic raw materials of the present invention
Dicyanovirazine (V) is DAMN and diketone (IV)
It is synthesized by reacting in water, alcohol, or organic acid. Here, RxSRy is R1, R z R s and R
, Rs and R. , Rff and R, and R, ~R. has the same meaning as above. Diketone (IV) is K. B
．． Sharpless, eL. a+. , Jour
nal of' the As+ericanChem
ical Scley. 93.3303 (1971)
It is manufactured by the conventionally known method described in et al. [Example] Next, the present invention will be further explained with reference to Examples. Example 1 50 ml3 with reflux condenser, thermometer and stirrer
2,3-dicyanosyl-dodecano[b.]pyrazine (Vl) in a Hertzian flask.1. 0g (3.7
mmol) and methanol lO-, refluxed once to ensure complete melting, and then 61 tp, DBU0
．． 34 ml (2.3+*mol) was added using a graduated pipette. The mixture was stirred and refluxed for 30 hours. After cooling, it was filtered and washed with methanol. This was separated using chloroform and licage-based lamb chromatography. Further, it was recrystallized with 300 times the amount of chloroform-ethanol (V/V 5 : 7) rJR mixture to obtain blue extremely small needle-shaped crystals [■]. Yield: 0.19g (yield: 18%). IR:
3270, 2900, 1550.1510cm -'U
V-VrS: 342,621,655nm (solvent, chloroform)'H-NMR: -1.061)
1111 (3,2B), 1.30 ~ 1.82ppm
(m,48}1). 2.40-2.52pp■ (steel, 1611), 3.62ppm (t, 1.6I+
) MS, H+ 1075 (Mri-1075.5)
Elemental analysis: C. 70.26 (70.30), H;
7.54 (7.74). N. 20.49 (20.50
)% Calculated values in parentheses, (however, [■] is monohydrate C64HI
Calculated as ANl&O. ) Solubility in chloroform (room temperature): 3.2xlO-'sol/1 or because it effectively absorbs visible light, it can be used for optical recording media, electrophotography, photosensitive materials for laser printers, redox catalysts, flowers, cut flowers, etc. It can be effectively used as a food freshness preserving agent. Application filed (430) Agent for Nippon Soda Co., Ltd. (7125) Yoshiyoshi Yokoyama (9648) Created by Yutaka Tokai [Effects of the invention]

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 hydrogen or adjacent 2 of pyrazine.
R_1 and R_2, R_3 and R_4
, R_5 and R_6, or R_7 and R_8 together form a ring having 6 or more carbon atoms. This ring may contain oxygen in the middle or may be substituted. However, R_1 to R_8 are not all hydrogen. M is
Indicates hydrogen (2H), metal, metal oxide, metal hydroxide, acyl metal, alkoxy metal, siloxy metal, or metal halide. ] A tetrapyrazinoporphyrazine compound represented by