JPS58198425A - Alpha-phenylstilbene derivative and preparation thereof - Google Patents

Abstract

NEW MATERIAL:An alpha-phenylstibene derivative expressed by formula I {A is formula II or III [(R)m are H, alkyl, alkoxyl, halogen, dialkylamino, aralkylamino or arylamino and may be the same or different when m is >=2; m is an integer 0, 1, 2 or 3], or 9-anthryl or N-alkylcarbazolyl; n is 0 or 1}. EXAMPLE:alpha-Phenyl-4'-N,N-dimethylaminostilbene. USE:An electrophotographic organic photoconductive material and fluorescent brightener. PROCESS:A 1,1-diphenylmethyl derivative expressed by formula IV [Y is triphenylphosphonium expressed by formula V (Z<-> is halogen ion) or a dialkyl phosphite expressed by the formula PO(OR1)2 (R1 is alkyl)] is reacted with an aldehyde compound expressed by formula VI to give the aimed compound expressed by formula I .

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel incorporation of α-phenylstilbene and a method for producing the same.

The α-phenylstilbene derivatives of the present invention can be used as organic photoconductive materials and fluorescent brighteners for electrophotography. In particular, it is useful as an organic photovoltaic material for electrophotography, as will be described later.

Conventionally, a large number of materials including polyJ-N-vinylcarbazole have been proposed as organic photoconductive materials for photoreceptors used in electrophotography.

The "electrophotographic method" referred to here generally refers to a method in which a photoreceptor is first charged in a dark place by, for example, corona discharge, and then an electrostatic latent image is formed by selectively discharging only the exposed areas. This is one of the image forming methods in which an image is formed by visualizing this latent image using a developing means using toner or the like. The basic characteristics required of a photoreceptor in such an electrophotographic method are: 1) being charged to an appropriate potential in a dark place, 2) having little discharge of charge in a dark place, and 3) being able to withstand light irradiation. Examples include discharging charges more quickly. However, the reality is that conventional photoconductive organic materials do not necessarily fully satisfy these requirements.

On the other hand, selenium and zinc oxide are known as photoconductive inorganic materials, and it is a fact that selenium is widely used in practical applications. However, recently, in terms of the electrophotographic process, many demands have been placed on the photoreceptor. For example, in addition to the above-mentioned basic characteristics, a flexible belt-like photoreceptor is also required in terms of shape. It's starting to look like this. However, in the case of selenium, it is generally difficult to form it into such a shape.

An object of the present invention is to provide a novel α-phenylstilbene derivative which is particularly useful as a photoconductive material and which eliminates the above-mentioned drawbacks of photoconductive materials for photoreceptors, and a method for producing the same. It is.

That is, the first invention is based on the general formula (+) (wherein R represents a hydrogen atom, a lower alkyl group, a lower alkoxy group, a halogen atom, a lower dialkylamino group, an aralkylamino group, or an allylamino group (7, X is represents a benzene ring, naphthalene ring or indole ring; n is an integer of 0-! or 'l; m is an integer of 0, 1.2 or 3) The second invention is a derivative, and the second invention is a triphenylphosphonium group represented by the general formula (If) (representing a halogen ion) or a derivative represented by P(-)(OR)2 (where R represents a lower alkyl group). A 1,1-diphenylmethyl derivative represented by 1, which is a dialkyl phosphite group represented by 1,] and the following general formula 7 (Ill) (wherein R, X, m and n are the same as the above definitions), The following general formula (1) (wherein R, X, m and n are as defined above) is reacted with an aldehyde compound represented by the following general formula (1).

) This is a method for producing an α-phenylstilbene derivative represented by:

The 1,1-diphenylmethyl derivative represented by the general formula (II) used in the present invention can be easily produced by heating the corresponding halomethyl compound and trialkyl phosphite directly or in a solvent such as toluene or xylene. be done.

Here, the trialkyl surface phosphate is preferably an alkyl group having 1 to 4 carbon atoms, particularly a methyl group or an ethyl group. An aldehyde compound represented by the formula (...) is heated from room temperature to 100°C in the presence of a basic catalyst.
As a basic catalyst at a temperature of about
Mention may be made of alcoholades such as caustic potash, sodium amide, sodium hydride and sodium methylate, potassium tert-butoxide.

In addition, as a reaction solvent, methanol, ethanol, inopropanol, butanol, 2-methquin ethanol,
l,2-dimethoxyethane, bis(2-methoxyethyl)ether, dioxane, tetrahydrofuran, toluene, xylene/,/methylsulfoxide, N,N-dimethylformamide, N-methylpyrrolidone, 1,3-dimethyl-2-imidazo Among them, polar solvents such as N,N-dimethylformamide and dimethylformhokind are preferred.

The reaction temperature is determined by 1) the stability of the solvent used with respect to the basic catalyst, 2) the reactivity of the condensation component (compounds of general formula (II) and (1)), and 3) the stability of the basic catalyst in the solvent. They can be selected from a wide range depending on their reactivity as condensing agents. For example, when using a polar solvent, the temperature is actually room temperature to 100°C, preferably room temperature to 80°C. but,
When the reaction time is shortened or when a condensing agent with low activity is used, the temperature may be even lower.

The novel α-phenylstilbene derivative according to the present invention is exemplified as follows. It is extremely useful as a photoconductive material and can be optically or chemically sensitized using a sensitizer such as a dye or a Lewis acid.1 It is also a so-called functionally separated photosensitive material that uses heavy pigments or inorganic pigments as charge-generating substances. It is particularly useful as a charge transfer agent in the body.

Examples of the above-mentioned sensitizers include triallylmethane dyes such as methyl violet and crystal violet, xanthine dyes such as rose bengal, erythrosine, and Rogue 7B, methylene blue, etc. [sigma] thiazine dyes, 2,4.7-dolinitro-9-fluorenone, 2, 4-dinitro-9-
Examples include Fluoreno 7.

The crushed organic pigment is CI Pigment Blue 25.
(CI A 21180), C.I. Pigment Blue 41 (CI Bian 21200), C.I. Basinoclenod 3 (CI J16.45210), etc., C.I. Pigment Blue 16 (CIA741)
00), indigo pigments such as C.I. Hatsuto Brown 5 (CI A 73410) and C.I. Hatsuto Dai (CI A 73030), and perylene pigments such as Argo Scarlet B and Indah/Thlen Scarlet R. I get kicked.

Father, selenium, selenium-tellurium, cadmium 6te, α
Inorganic pigments such as -Nrico/ etc. can also be used.

Next, the present invention will be explained in more detail with reference to Examples.

Example 1 1.1-diethyl diphenylmethylphosphonate 3,0
49 (0,010 mol) and 4-N-N-dimethylaminobenzaldehyde 1.49 f (0,010 mol)
was added to 20 ml of 1,2-dimethoxyethane, and 5
0.50 f of 0% sodium hydride was added. 3 at room temperature
After stirring for a period of time, the mixture was heated under reflux for 30 minutes. After cooling to room temperature, the reaction mixture was poured into 200 g of water, and the resulting precipitate was removed, washed with water, and dried. The yield is 2.02 (yield 6
6.7%) was recrystallized from ethanol to obtain a sample of α-phenyl-4'-N-N-dimethylaminostilbene in pale yellow plate-like crystals. Melting point is 125.0-12
The temperature was 5.5°C.

The elemental analysis values were as follows for C2□H2,N9, 0% H% N% Calculated value 88,24 7,08 4.68 Actual value
88.01 7.07 4.76 The infrared absorption spectrum (KBr tablet method) is shown in FIG. A novel α-phenylstilbene derivative was obtained by repeating the same procedure as in Example 1 except that the aldehyde shown in iQ was used.

The results are shown in Table 1.0. Figure 2 shows the infrared absorption spectrum (KBr tablet method) of α-phenyl-4'-N-N-dibenzylaminostilbene obtained in Example 4. 4'-N-N'
- The infrared absorption spectrum (KBr tablet method) of diphenylaminostilbene is shown in Figure 3, and the infrared absorption spectrum of 1,1-diphenyl-2-(3-N-ethylhalazoryl)ethylene obtained in Example IB+ to (KBr tablet method) is shown in Figure 4. .

Example 15 1.1->Phenylmethylphosphonium bromide 5
．． 09 f (0.01 mol) and 2.742 (001 mol) of 4-N-N-diphenylaminobenzaltehyde were added 20 g of N-N-dimethylformamide, and to this was added 28 methanol solution of sodium methylate. .90f
was added dropwise over 130 minutes at 22 to 28C.After the addition, the mixture was stirred at room temperature for 6 hours, and then diluted with 50C of water. After extracting the product with toluene, the organic layer was washed with water, dried, the toluene was removed, and a small amount of ethanol was added to crystallize it.
Recrystallization from a hexane-toluene mixed solvent gave α-phenyl-4'-N-N-diphenylamine stilbene 5.79r (yield 65%) as pale yellow needle crystals. The melting point was 940-950°C.

The pressure analysis value, C3□H25N, was as follows. .

0% H% N coefficient calculated value 9073 5.96 331 Actual value 90
48 5.91 3.19 Infrared absorption spectrum (K
Br tablet cutting method) was consistent with FIG. 3 obtained in Round Example 8.

.

[Brief explanation of drawings]

Figure 1 shows the compound obtained in Example 1, Figure 2 shows the compound obtained in Example 4, Figure 3 shows the compound obtained in Example 8, and Figure 4 shows the compound obtained in Example 1O. Infrared absorption spectra of each of the obtained compounds (KBr tablet cutting method) 1゜Patent applicant: Hide Komatsu, attorney for Ricoh Co., Ltd. Procedural amendment filed on May 26, 1980, Commissioner of the Japan Patent Office, Haruki Shimada 3. Relationship between the supplement and the heir case Patent applicant 4, agent 107 (Telephone: 586-8854)
)8? Contents of the Article (Attachment) 1. The scope of the claims starting from line 5 on page 1 of the specification. The following corrections are made. [2.Claim 1, General formula (1), R is a hydrogen atom, a lower alkyl group, a lower alkokene group, a halogen atom, a lower dialkylamino group, substituted or unsubstituted Indicates an aralkylamino group or an unsubstituted allylamino group. n is 0 or an IQ integer, m is 0. l is an integer of 2 or 3. ) li The α-phenylstilbene derivative that is often used in public. 2 General formula (1) is a lertriphenylphosphonium group represented by a halogen ion) or a dialkyl phosphorous group represented by l'o (OR>2 (where R represents a lower alkyl group)6) The 1,1-diphenylmethyl derivative coated with the following general formula (■1) OHC-(-CH2CH-)TΔ...
II) (wherein A, RXm and n are the same as defined above). (as defined in Section 1.) A method for producing an α-phenylstilbene GH conductor represented by 2. Correct 1j from page 5, line 10 to the last line as follows. . 9-An) IJ group represents an unsubstituted or unsubstituted N-alkylcarbazolyl group, and R is a hydrogen atom, a lower alkyl group, a lower alkoxy group, a hydrogen atom, a lower dialkylamino group, or侠 or r [represents an unsubstituted aralkylamino group or a substituted or unsubstituted allylamino group, n is an integer between 0 and 1, m is an integer between 0゜, 2 or 3)'' 3 , From the bottom of page 6, lines 4 to 2 are corrected as follows. . r OHC+CH=CH+-A...
...(lit) (In the formula, A, RXm and 11 are the same as the above definitions.)" 4, page 7, lines 3 to 5 are corrected as follows. (In the formula, A, RXm, and n are as defined above.) 5 From the 7th Sada-F, the 9th line [...trialkyl]
should be corrected as [...trialkyl or triphenylphosphine]. 6. Correct "sample" on page 13, line 13 to "genuine product". Procedural amendment dated October 22, 1980 Kazuo Wakasugi, Commissioner of the Patent Office1, Indication of the facts, Patent Application No. 1980-801152, Title of the invention: α-Phenylstilbene derivatives and their Ill.3, Supplementary Il. :Relationship with the case of the person who applied for the patent (674) Ricoh Co., Ltd. -5, Date of amendment order (voluntary) 6, Particulars of the subject matter of the amendment -, Detailed description of the invention - and drawings (Figure 5)
(Attachment) 1. [Examples 2 to 141 in the 14th line of the specification, line 3] are corrected to Examples 2 to 15J. 2. Add the following data to each - in Table 1 on page 16 as data for Example 15. Example No. I'15J Aldehyde used [α-phenylstilbene derivative melting point ('C) r 139.0-140. OJ(
Easily re-solidified soluble 111) r (dioxane-ethanol) j Elemental analysis value (%) Actual value/calculated value C'・HN r 90.31 6,50
3.07/90.41/6.49
/ 3.10 J3, the 17th true “Example 15” was corrected to “Example 17”, and this “Example 1
7", the following 1st Example 16" is added. [Example 16 Diethyl 1.1-shifugol methylphosphonate 6.50
g (0,02+ mol) and 4-N,N diphenylaminobenz)aldehyde 5.84(] (00,021
moles of N,N-dimethylformaldehyde 40
Potassium-1-butoxide 2 is dissolved in mβ.
．． 8312 (0,025 mol) at 21-33℃
It took 0 minutes to add. After the addition, the reaction mixture was stirred at room temperature for 4 hours, and the resulting precipitate was collected by filtration, washed with water, and dried to yield 8.20Q (yield: 90.6%).
) was obtained. Then, after recrystallization from a toluene-ethanol mixed solvent,
The obtained pale yellow needle crystals were collected by filtration, washed with methanol, and then dried to obtain pure α-phenyl-4=-N,N-diphenylaminostilbene. Melting point is 94.0~
95. It was O'C. The elemental analysis value was as follows as 032 H25N. 0% 8% N% actual measurement 1a 90
．． 68 5.91 3.32 Total sieve value 90.73
5.96 3.31 Infrared absorption spectrum (KB
Tablet method> is shown in FIG. j 4, recrystallize from 1 mixed solvent in line 6 from the bottom of page 17, C
] should be corrected to "recrystallize from a mixed solvent, wash with methanol, and then dry." 5. In the 4th and 5th lines of page 18, "Infrared absorption spectrum... matched with Figure 3."
The infrared absorption spectrum (KBr method) was consistent with FIG. 5 obtained in Example 16. ” he corrected. 6, page 18, line 10, change “compound” to [compound, 1
Correct. 7. Insert "[Figure 5 shows the compound obtained in Example 16]" between lines 10 and 11 on page 18. 8. Add attached Figure 5 to the drawings. Above procedure amendment type January 11, 1980 Director-General of the Patent Office Kazuo Wakasugi 1, indication of TLFL Patent application 1982-8011
No. 5, No. 2, Title of the invention α-7 enylstilbene derivative and its manufacturing method 3, Relationship with the case of the person making the amendment Patent application Name of person
(674) Co., Ltd.] - 4, Agent 6, Subject of amendment 1, Procedural amendment sheet submitted on May 26, 1980, No. 1
The scope of claims written in the negative statement on page 3 is corrected as follows. 12, Claim 1, General formula (I) represents a 9-anthryl group or a substituted or unsubstituted N-alkylcarbazolyl group, R is a hydrogen atom, a lower alkyl group, a lower alkoxy group, a halogen atom, a lower The dialkylamino group, substituted or unsubstituted 7-ralkylamino group, or substituted or unsubstituted is an integer of 1, and is an integer of 0.1.2 or 3. ) An α-rough l nylstilbene conductor represented by: 2. A triphenyl small sulfonium group or PO(OR)2 represented by the general formula (II) (ze represents a herogion) (where R represents a lower alkyl group)
It is a dialkyl bent phosphoric acid group represented by ] A 1,1-diphenylmethyl derivative represented by the following general formula (III) α- represented by the following general formula (T) (wherein A, R, ■ and n are as defined above), characterized by reacting with an aldehyde compound represented by A method for producing a 7-enylstilbene derivative. ” 2. In the same procedure amendment garden, page 4, line 2, [allylamino group is replaced with “
arylamino group”. 1 Procedure? …J Book February 24, 1980 Kazuo Wakasugi, Commissioner of the Patent Office 1. Indication of the case: Japanese Patent Application No. 57-80115 2. Name of the invention α-Rough 1 Nilstilchen conductor and its manufacturing method 3. Stone for amendment Relationship to the incident Special revision application Person’s name
(674) Rico-4 Co., Ltd., Agent: 107 (Telephone: 586-8854) Address: 4-13-5-5, Hanaita, Minato-ku, Tokyo, Amended Order [1-1 (Voluntary)] (including procedural amendments), claims and details of the invention 1, procedural supplement 11 submitted on January 11, 1988;
The claims stated on pages 1 to 3 are corrected as stated in 1. [2, Claim 1, General formula (T) 9-anthryl group or substitution or! Represents a substituted N-alkylcarbazolyl group, where R is a hydrogen atom, a lower alkyl group, a lower 2l]1cy group, a halogen atom, a lower dinolgylamim 1,1-substituted or unsubstituted ? It represents a ralkylamino group or a substituted or unsubstituted arylamino group, and when m is 2 to 11-, they may be the same group or different groups. n is an integer of 0 or 1; - is an integer of 0.1.2 or 3; ) An α-7I nylstilbene derivative represented by: 2. Triphenylphos j1-ium group represented by the general formula (II) (Z'' represents a halogen ion) or PO(OR+)2 (
Here, R+ represents a lower alkyl group) dialkyl sub-phosphorus lIIm! It is. The 1,1-Schiff I nylmethyl derivative represented by 1 and the following general formula (III) OHC+ CH= CH+ n A --(III)
9-7thlyl group or substituted or unsubstituted N-alkylcarbazolyl group, R is a hydrogen atom, lower alkyl group, lower nosyl]oxy group, halogen atom, lower diflukylamino group, substituted or unsubstituted represents a substituted aralkylamino group or a substituted or unsubstituted arylamino group, and when the number of cranes is 2 or more, they may be the same group or different groups. +1 is an integer of 0 or 1, - is an integer of 0.1.2 or 3. ) The following general formula (1) (wherein A and 0 are -[
As defined in . ) A method for producing an α-phnylstilbene derivative represented by: 1 2, Details 1, 6th line, 8th line rPo (OR) 2 J to l
Po (OR1) 21 and 81 correct, I' in parentheses
Correct RJ to rRlj. 3. Procedural amendment 1 submitted on May 26, 1981, page 4, line 8 and line 13 [where A, R1 theory and nj are replaced with "
A and n' in the formula. The above 13 continuations...jh book 1978' = 1311 rs Or + special. 1st Office Officer
Kazuto Sugi 1, $1'10 Table Small Patent Application 1980-80115 2) Name of the Company (Chi-7 Enylstilbene Induction IA Continuation Production 1:, '4iI. 3, Supplementary Materials) 111 to <1 B) Relationship with Old Police 1'1 Special Agreement Application Person Name (674) Stock Association
1-4, 3111 people 5, supplement 11 date of order (voluntary) 6, supplement it
Pair 9 In the specification, the column for detailed description of the invention (
Attachment) 1. Details, 1st 14v4 3rd Homare 1 “Example 2-154
(Including the first amendment submitted on October 220, 1972) was revised 11 to 1 implementation 1l112-191. 2. Implementation of Table 1 on page 16 @ Add the following after 15 +
31+. Procedural amendment April 7, 1980 Kazuo Wakasugi, Director General of the Patent Office 1, Indication of the case Special No. 1980-80115 2,
Title of the invention α-Phenylstilbene derivatives and their manufacturing process 3, Amendment (1) Relationship with the applicant Name (674) Ricoh Co., Ltd. 5, Date of supplementary order (voluntary)

Claims (1)

[Claims] 1. General formula (1) (wherein R represents a hydrogen atom, a lower alkyl group, a lower alkoxy group, a halogen atom, a lower dialkylamino group, an aralkylamino group, or an arylamino group, an Xβ benzene ring, (representing a naphthalene ring or an indole ring; n is an integer of 0 or l; m is an integer of 0, 1.2 or 3). A phenylphosphonium group represented by 2 general formula (II) (indicates a rogene ion) or a dialkyl phosphorous group represented by PO(OR)2 (where R represents a lower alkyl group). ] The 1,1-diphenylmethyl derivative represented by is reacted with the aldehyde compound represented by the following general formula (II) (wherein R + X r m and n are the same as defined above) A method for producing an α-7 enyl stilpene derivative represented by the following general formula (1) (wherein R, X, m and n are as defined above).