JPS62267256A - Novel tetrazonium salt compound and production thereof - Google Patents

Abstract

NEW MATERIAL:A compound expressed by formula I (X is anionic functional group). EXAMPLE:1,8-Bis(4-nitrophenyl)-1,3,5,7-octatetraene. USE:A synthetic intermediate for bisazo compounds which are organic photoconductors used in electrophotographic photosensitive materials, particularly laminated type photosensitive materials capable of exhibiting high sensitivity for high-speed cameras and laser printers. PREPARATION:1,8-Bis(4-nitrophenyl)-1,3,5,7-octatetraene expressed by formula II is reduced in the presence of a reducing agent, e.g. iron-hydrochloric acid, etc., in a solvent, e.g. N,N-dimethylformamide, etc., at 70-120 deg.C to give a compound expressed by formula III. Sodium nitrite is then added to expressed by formula III. Sodium nitrite is then added to diazotize the compound expressed by formula III at -10-+20 deg.C to afford the aimed compound expressed by formula I.

Description

Detailed Description of the Invention Technical Field The present invention relates to a novel tetrazonium salt compound and a method for producing the same, and more particularly to a tetrazonium salt compound that is an intermediate for producing a bisazo compound useful as an organic photoconductor and its production. Regarding the method.

PRIOR ART Traditionally, organic photoconductors used in laminated photoconductors, which are a type of electrophotographic photoconductor, have been made of certain azo compounds.
It is known that it is particularly useful as a charge-generating pigment. As is well known, this laminated photoreceptor consists of a charge generation layer containing a charge generation M material as a main component having the ability to generate charge carriers by light on a conductive support, and a charge generation layer containing charge carriers generated in the charge generation layer on top of the charge generation layer. This photoreceptor is provided with a charge transport layer containing a charge transport material as a main component, which has the ability to efficiently inject and transport the charge transport material. Conventionally, examples of azo compounds used in such photoreceptors include those disclosed in Japanese Patent Application Laid-Open No. 47-37543.
benzidine-based bisazo compounds described in JP-A-52-55643, etc.; stilbene-based bisazo compounds described in JP-A-52-8832;
Known examples include diphenylhexatriene-based bisazo compounds described in Japanese Patent Application Laid-Open No. 222152-222, and diphenylbutadiene-based bisazo compounds described in JP-A-58-222153.

However, conventional laminated photoreceptors using azo compounds generally have low sensitivity and are unsatisfactory as photoreceptors for high-speed copying machines. On the other hand, in recent years, there has been a desire to develop a high-sensitivity photoreceptor that can cover the wavelength range of semiconductor lasers, especially as a photoreceptor for laser printers.1. The reality is that the above-mentioned laminated photoreceptor cannot meet this purpose for the same reason.

Purpose The purpose of the present invention is to provide a highly sensitive electrophotographic photoreceptor that is practical not only for high-speed copying machines but also for laser printers.
The object of the present invention is to provide a tetrazonium salt compound which is an intermediate for producing a bisazo compound useful as an organic photoconductor used particularly in a laminated photoconductor, and a method for producing the same.

Structure One of the present invention is a tetrazonium salt compound represented by the general formula Iは2■ 0, Nsha OH: OH), +No.

1,8-bis(4-nitrophenyl)-1,
3,5,7-octatetraene is reduced to give 1,8-bis(4-aminophenyl)-1,
This is a method for producing a tetrazonium salt compound represented by the general formula (1), which is characterized in that 3,5,7-octatetraene is prepared and then diazotized. Here is the general formula 1
Representative examples of the anionic functional group X in are 07e,
Bre.

Io, BF′? , PFp , B((3,H,)?
, O1O? , 80n.

Or rather, BF? It is.

The tetrazonium salt compound of the present invention represented by the general formula 1 is a useful intermediate for obtaining the bisazo compound represented by the following general formula 1 formed by a coupling reaction with Cassirer.

Ar-N=N+ 0H=OH) building N=N-Ar (tv
) [However, Ar is ArH (for example, an aromatic hydrocarbon compound having a hydroxyl group and/or an amino group; a heterocyclic compound having a hydroxyl group and/or an amino group; an aliphatic or aromatic enolic ketone group) (i.e., a compound having an active methylene group, etc.). ] Next, the method for producing the tetrazonium salt compound of the present invention will be explained. First of all, 1.8 of the Nishin used in this manufacturing method.
-bis(4-nitrophenyl)-1,3,5,7-octatetraene, for example, 4-nitrocinnamyltriphenylphosphonium bromide and 5-(4-nitrophenyl)-2,4-pentagenal- 1 and condensed in the presence of a basic catalyst, which is the so-called Witteig reaction. The dinitro compound (1) produced by this reaction contains a portion of the 3-monocysate, which is obtained from the reaction crude product as it is or after purification, and contains aromatic hydrocarbons such as toluene and xylene together with iodine in the catalyst. It can be converted to the all-trans form by heat treatment in a system solvent.

Next, the 1,8-bis(4-nitrophenyl)-1,3,5,7-octatetraene obtained in this way is usually reduced by reducing iron-hydrochloric acid, tin-chloride monohydrochloride, etc. The reaction is carried out by heating to a temperature of 70 to 120° C., and the reaction is completed in about 0.5 to 3 hours. In addition, when an iron-hydrochloric acid reducing agent is used, it is preferable to carry out the reaction in an organic solvent such as N,N-dimethylformamide.

Furthermore, the dinitro compound (11) obtained as above
and diamino compound (II) are both new substances.

Next, the diazotization of the 1,8-bis(4-aminophenyl)-1,3,5,7-octatetraene obtained in this manner is carried out by diazotizing this diamino compound (I) with an inorganic acid such as hydrochloric acid or sulfuric acid. The reaction is completed in about 0.5 to 3 hours.

Due to this reaction, the general formula! By further adding an aqueous solution of borohydrofluoric acid, sodium borofluoride, etc. to this diazotization reaction solution for salt conversion, a tetrazonium salt of the general formula Natsu can be obtained.

The present invention will be explained below using examples and application examples.

Example 1.8-bis(4-nitrophenyl)-1,3,5,7
-: Production of octatetraene 4-nitrocinnamyltriphenylphosphonium bromide 315F and 5-(4-nitrophenyl) -2,
4-Pentagenal-1: 117f% dry methanol 5101 to dry dimethylformamide (DMF) 64w
The solution was placed in a mixed solvent of 300 ml, and 1 & 6 t of a 28-timethanol solution of sodium methoxide was added dropwise over 2 hours under a N gas flow to react. Then, the reaction solution was stirred at room temperature for 6 hours, and then diluted with 50% methanol aqueous solution.

-, the precipitate was filtered, washed with water, and dried to obtain 1.8-bis(4-nido-o7z-nyl)-1 containing the 3-monocis form.
,3,5,7-octatetraene crude product 19.9f%
Obtained. Next, this was mixed with xylene 5oo-
After heating to reflux in
"Dark red needle crystals of e5e7-octatetraene 149
t (yield 69%) 8 was obtained. mp, 2315-240.
5℃.

Elemental analysis (as 0, H, Horse 04): OHN Actual value ('%) 68.77 463 7.
91 calculation body (%) 6 & 95 464 I
LO4 visible spectrum (in DMF): λmax, 439 am The infrared absorption spectrum (KBr tablet method) of this product is shown in Figure 8. As you can see from this diagram, 1510cnr-”
Absorption power j1 based on the stretching vibration of the nitro group was observed at 133&', and absorption based on the out-of-plane bending vibration of the trans olefin was observed at 1010 and 950 cm-''.

1.8-bis(4-aminophenyl)-1,3,5,7
-Production of octatetraene 1,8-bis(4-nitrophenyl)-t,s,5.7-octatetraene IL obtained as described above
28 f% DMP250Wtl and add 2L of iron powder to it
After adding 5 f, 561 of concentrated hydrochloric acid and 19 of water were added under stirring.
Dilute hydrochloric acid consisting of - was added, and stirring was continued at 80 to 88°C for an additional 5 hours. After cooling at 50° C., the mixture was made alkaline by adding a 10% aqueous solution of caustic soda, and the insoluble portion was heated and filtered with Celite. Fff'i - Diluted with water, precipitated crystal 8 was filtered, washed with water, and dried to obtain 7.9 f (yield: 85 g) of diamino compound. This% was recrystallized from a mixed solvent of DMP and water, and l,8-bis(4-aminophenyl)-1,3
, 5,7-octatetraene were obtained as dark red plate-like crystals.

mp, 2615-264.5°C.

110- Elemental analysis (as C wholesale H, N): OHN Actual value book) 8 & 01 7.02 9.75 Calculated value) 83.28 7.00 9.71 The infrared absorption spectrum of this product is shown in Figure 2. Shown below. As can be seen from this figure, absorption based on the stretching vibration of the primary amine was observed at 3450 to 3200 cm'', and absorption based on the out-of-plane bending vibration of the trans-olefin was observed at 10101O and 955 m''.

1,8-bis(4-aminophenyl)-1,3,5,7-octatitraene 6.1f obtained as described above
The mixture was added to dilute hydrochloric acid consisting of 7.21 parts of concentrated hydrochloric acid and 100 parts of water, and stirred at 60°C for 2 hours.

After quenching to -2°C, sodium nitrite 3.23 f
A solution prepared by dissolving . Thereafter, the mixture was stirred at the same temperature for 20 minutes, and after adding 400 g of cold water, a trace amount of insoluble material was removed by filtration, and the p-liquid crystal F was removed. %) was obtained.

The infrared absorption spectrum of this product is shown in FIG. As can be seen from this figure, absorption based on the stretching vibration of the diazonium salt was observed at 2230 cm-'.

Application Examples A bisazo compound represented by the following formula (2) was synthesized by coupling the tetrazonium salt obtained in the example with a coupler represented by the following formula V.

Next, this bisazo compound (as a charge generating substance) 7.5
Part and polyester resin [■Noseiron 20 manufactured by Toyobo Co., Ltd.
500 parts of a 0.5% tetrahydrofuran solution of 0] was ground and mixed in a Zeel mill, the resulting dispersion was applied onto an aluminum-deposited polyester film with a doctor blade, and air-dried to form a charge generation layer with a thickness of about 1 pWL. was formed. Next, 9-ethylcarno as a charge transport material? Two parts of sol-3-aldehyde-1-methyl-1-phenylhydrazone were dissolved in a 10% tetrahydrofuran solution of a polycarbonate resin (Panrai K-1300) manufactured by Yojin Co., Ltd., and this solution was doctored onto the charge generation layer. It was applied with a blade and dried at 80° C. for 2 minutes and then at 120° C. for 5 minutes to form a charge transport layer with a thickness of about 20 μm.

Next, in order to examine the sensitivity in the visible range of the laminated electrophotographic photoreceptor obtained in this way, this photoreceptor was tested at 16 KV in a dark place using an electrostatic copying paper tester [■Tsukichi Denki Seisakusho #SF42g model]. After charging by performing corona discharge for 20 seconds, dark decay was performed for 20 seconds, and the surface potential To
(/lt), and then the illuminance on the photoconductor surface is 4.5.
The time (s
ee), and the half-reduced exposure tE'/ as the sensitivity in the visible range.
2 was 0.49jux*sec.

Further, the following measurements were conducted to examine the sensitivity of this photoreceptor to long wavelength light. First, the photoreceptor is charged by corona discharge in a dark place, and then the surface potential decreases to 8 due to dark decay.
At the time when 0.00000000000000000000000000000000000000000000000000000000000000000000000000000000000000 had since now showed 000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000 results., a monochromatic light of 780 nm was irradiated with monochromatic light of 780 nm. Next, the time (8) until the surface potential attenuates to 1/2 (400/rut) is determined, and then the exposure time t (PW-
@ m cIn-2) and the light decay rate 5 (voIt
-d-PJ″″1) was calculated. The result is S=58
0 V *d・PJ-” “C’ Atta.

Thus, it can be seen that the photoreceptor using the bisazo compound derived from the tetrazonium salt compound of the present invention has extremely high sensitivity not only in the visible region but also in the semiconductor laser region.

Effects As can be seen from the above explanation, the tetrazonium salt compound of the present invention can be used in electrophotographic photoreceptors that exhibit high sensitivity both for high-speed copying machines and laser printers, especially for contact photoconductors used in laminated photoreceptors. It is extremely useful as an intermediate for bisazo compounds.

[Brief explanation of drawings]

Figures 1 to 2 show infrared absorption spectra of dinitro compounds and diamino compounds, which are intermediates for obtaining the tetrazonium salt compounds of the present invention, and Figure 3 shows infrared absorption spectra of the tetrazonium salt compounds of the present invention. Special applicant Rico Co., Ltd. - Procedural amendment July 10, 1986 Director of the Patent Office Michibe Uga 3, person making the amendment Relationship to the case Patent applicant 1-3 Nakamagome, Ota-ku, Tokyo No. 6 (674) Ricoh Co., Ltd. Representative Hama 1) Hiro 4, Agent 4-5 Kojimachi, Chiyoda-ku, Tokyo (102) 5 Subject of amendment 6 Contents of amendment 1) Scope of claims attached. Correct it as follows. 2) 2nd line r1335-J from the bottom of page 9 of the specification r 1
Corrected to 335an-1J. 3) Correct ran'J on page 11, line 7 to ran-1J. 4) Page 11, line 8 rlo10an” and 955aa
Correct J to rloloan-1 and 955an-J. 5) On page 11, line 14, "concentrated hydrochloric acid" is corrected to "concentrated sulfuric acid." 6) On page 11, line 15, "dilute hydrochloric acid" is corrected to "dilute sulfuric acid." 7) Page 11, lines 7-8 r E 1/2 is 0.49
It was 1ux-sec. ” to “El/2 (lux-8
ec) was calculated. As a result, Vo is 533 volts, and E1/2 is 0.4
91ux"see." 7. List of attached documents (1) Attachment 1 separate sheet
Paper Claim 1: A tetrazonium salt compound represented by the general formula (Xo.N2@+CH= CH)4+ N2Φ.Xo (or an anionic functional group). 2, 1,8-bis(4-nitrophenyl)-1, represented by the formula ■ o2N-4CH=CH), unit No.2
3,5,7-octatetraene is reduced to form the formula ■N2N(
■CH=CH) 4 units NH2 1,8-bis(4-aminophenyl)-1,
3,5,7-octatetraene, which is then diazotized.
A method for producing a tetrazonium salt compound represented by H=CH)4+Nz...Xe (where X represents an anionic functional group).

Claims (1)

[Claims] 1. A tetrazonium salt compound represented by the general formula ▲ Numerical formula, chemical formula, table, etc. ▼ (where X represents an anionic functional group). 2. Formula II ▲There are mathematical formulas, chemical formulas, tables, etc.▼ 1,8-bis(4-nitrophenyl)-1,
3,5,7-octatetraene is reduced to produce 1,8-bis(4-aminophenyl)-1, which is represented by formula III ▲Mathematical formula, chemical formula, table, etc.▼
A tetrazonium salt represented by the general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (where X represents an anionic functional group), which is characterized by forming 3,5,7-octatetraene and then diazotizing it. Method of manufacturing the compound.