JPH11302258A - Benzazepine derivative having ethenyl group - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new compound capable of providing a polymer useful as a material for an electrophotography, or the like and having excellent hole- transport properties, and having a specific nitrogen-containing seven-membered structure. SOLUTION: This new compound is the compound of formula I [(A) is vinylene or o-arylene; R1 to R3 and Y1 to Y3 are each H or a substitutable group, with the proviso that at least one of the Y1 to Y3 is ethenyl; (n) is 0-4; with the proviso that when (n) is 0, the Y3 is an alkyl, ethenyl or an aryl], e.g. a compound of formula II. The compound of formula I in which Y1 or Y2 is ethenyl and (n) is 0 is obtained by brominating or iodizing a compound of formula III, reacting the obtained product with a compound of formula IV (Ra , Rb and Rc are each H or an alkyl; X1 is a trialkyltin, lithium or the like) in the presence of a palladium or nickel catalyst, and further reacting the product with a compound of the formula Y3 -Cl. A polymer derived from the compound of formula I has a high carrier-transporting ability, and when used as an electrophotography or the like, the polymer contributes to high sensitization or the like.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a benzazepine derivative. More specifically, the present invention relates to a benzazepine derivative having a vinyl group which can be a raw material of a polymer useful for an electrophotographic material or a coating-type organic electroluminescence (EL) material.

[0002]

2. Description of the Related Art Around 1970 Shattuck Schaffert (IBM
Et al.) And poly-N-vinyl carbazole (PVK)
Only by using a charge transfer complex of 4,7-trinitrofluorenone (TNF), a high-sensitivity organic photoconductor (OPC) comparable to the Se photoconductor has been realized (US Pat. No. 3,484,237, IBM). .J.Res.Develop, 15,75
(1971). This photoreceptor was applied not only to copiers but also to the first high-speed laser printers.

[0003] Thereafter, a new two-layer structure (charge generation layer (CG
L), a charge transfer layer (CTL) organic photoreceptor was developed. This method can be designed using an organic material without using Se or the like. Therefore, there is much room for material selection, and high sensitivity can be achieved. Therefore, this two-layer structure is currently employed in most OPCs. In addition to the function of moving the photocarriers efficiently, CTL also controls the properties such as printing durability (life) and environmental resistance of the photoreceptor as a surface layer, so it is necessary to select a material that satisfies all of them.

[0004] Therefore, CTL is divided into two methods: a method in which a low-molecular compound having charge transfer properties for carrier transport is blended into a polymer having mechanical strength, and a method in which a charge transfer polymer itself is used. Mainly formed. In the latter method, PVK is used, but the performance is insufficient, so the former method is currently widely used. However, if there is a polymer having better charge transfer ability than PVK, the design of the OPC will be simplified and it will be advantageous in terms of cost. Therefore, development of a new polymer type charge transport material has been strongly desired.

[0005] Organic electroluminescent elements are roughly classified into a vapor deposition type and a coating type. In the latter case, it is also called a wet type, and a thin film is formed by spin coating. As the dispersant, a carrier-transporting polymer is often used. A typical example is PVK, in which an electron transporting compound or a luminescent agent is dispersed and applied. (Applied physics
61 1044 (1992), Appl. Phys. Lett. 67, 2281 (1995), etc.). This method can simultaneously and simply dope a plurality of dopants as compared with the vapor deposition method, is advantageous when producing a white light emitting device, and is advantageous in device stability because it is a polymer and has a high glass transition point. Although the advantages are large, the performance of the carrier transporting polymer such as PVK is still insufficient, and the development of a more excellent carrier transporting polymer has been strongly desired.

[0006]

SUMMARY OF THE INVENTION Accordingly, the present inventors
In order to develop a polymer with excellent hole transport properties, we conducted research to find new monomer structures.

[0007]

As a result, it has been found that a polymer derived from a vinyl monomer having a nitrogen-containing seven-membered ring structure has an excellent hole transporting ability. The present invention has been made based on the findings. That is,
An object of the present invention is to provide a novel compound, and has been achieved by a vinyl compound having a benzoazepine structure represented by the general formula (I).

[0008]

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In the formula, (A) represents a vinylene or o-arylene group. At least one of Y ₁ , Y ₂ and Y ₃
One represents an ethenyl group, and R ₁ , R ₂ , R ₃ , Y ₁ , Y
₂ and Y ₃ represent a hydrogen atom or a substitutable group.
Here, n represents an integer of 0 to 4. When n is 0, Y ₃ is an alkyl group, an aryl group or an ethenyl group.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the compound represented by formula (I) of the present invention will be described in detail. In the general formula (I) of the present invention, the above-mentioned groups represented by (A), R _{1 to} R ₃ , Y ₁ , Y ₂ and Y ₃ have not only substituents but also substituents As long as it is possible, those having a substituent thereon are also included. (A) in the general formula (I) is a substituted or unsubstituted vinylene or o.
-Arylene, but specific examples of these unsubstituted groups are, for example, the following groups.

[0011]

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The substituent which (A) can have is a substitutable group defined by R _{1 to} R ₃ described below.

(A) is preferably a substituted or unsubstituted vinylene or o-phenylene group.

In the general formula (I), R _{1 to} R ₃ represent a hydrogen atom or a substitutable group. Substitutable groups are described in detail as follows: halogen atom, alkyl group, alkenyl group, aryl group, heterocyclic group , Cyano group, hydroxy group, nitro group, carboxyl group, sulfo group, amino group,
Alkoxy group, aryloxy group, acylamino group, mono- or dialkylamino group, N-unsubstituted, alkyl or aryl arylamino group, ureido group, sulfamoylamino group, alkylthio group, arylthio group, alkoxycarbonylamino group, sulfone Amido group, carbamoyl group, sulfamoyl group, sulfonyl group, alkoxycarbonyl group, heterocyclic oxy group, azo group, acyloxy group, carbamoyloxy group, silyloxy group, aryloxycarbonylamino group, imide group, heterocyclic thio group, sulfinyl group , A phosphonyl group,
Examples include an aryloxycarbonyl group, an acyl group, a silyl group, and an azolyl group. R _{1 to} R ₃ are not necessarily limited to one on each benzene ring, and a plurality of R _{1 to} R ₃ may be present.
In this case, the groups may be different or the same.

Preferred R _{1 to} R ₃ are a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, a dialkylamino group, an N-alkyl-N-
An arylamino group or a diarylamino group, specifically, a hydrogen atom, a halogen atom such as fluorine, chlorine or bromine, a substituted or unsubstituted carbon atom
Straight-chain or branched-chain alkyl group, substituted or unsubstituted C6-C20 aryl group, substituted or unsubstituted C1-C6 alkoxy group, substituted or unsubstituted C6-C20 Aryloxy group, substituted or unsubstituted dialkylamino group having 2 to 16 carbon atoms, substituted or unsubstituted N-alkyl-N- having 7 to 21 carbon atoms
Arylamino group, or substituted or unsubstituted carbon number 1
2 to 36 diarylamino groups.

The hydrogen atom and the halogen atom will be described in more detail. Methyl, ethyl, n-propyl, n-propyl
-Octyl, n-dodecyl, 2-methoxyethyl, 2-
Alkyl groups such as phenylmethyl, benzyl, isopropyl, isobutyl, sec-butyl, t-butyl, t-amyl, t-octyl, cyclopentyl, cyclohexyl or cycloheptyl, phenyl, 2-, 3- or 4-methylphenyl; 4-t-butylphenyl, 4
-Methoxyphenyl, 4-dimethylaminophenyl, 1
-Or 2-aryl groups such as naphthyl, anthryl or phenanthryl, methoxy, ethoxy, n-
Alkoxy groups such as propoxy, n-butoxy, n-hexyl, isopropoxy, isobutoxy, t-butoxy, cyclopentyloxy or cyclohexyloxy, phenoxy, 2-, 3- or 4-methylphenoxy, 4-t-butylphenoxy Aryloxy groups such as 4-phenylphenoxy, 4-methoxyphenoxy, 2-cyclohexylphenoxy, 3-ethylphenoxy, 1- or 2-naphthoxy, anthryloxy or phenanthryloxy, dimethylamino, diethylamino, dibutylamino , Dioctylamino, N-
A dialkylamino group such as methylbutylamino, bis (2-methoxyethyl) amino or bis (2-chloroethyl) amino; and an N-alkyl- such as N-methylanilino, N-butylanilino or N-methyl-1-naphthylamino. N-arylamino group, diphenylamino, N- (3-methylphenyl) anilino, N-
It is a diarylamino group such as (4-methylphenyl) anilino, bis (4-methylphenyl) amino, N-naphthylanilino, or dinaphthylamino.

Particularly preferred R _{1 to} R ₃ are a hydrogen atom or an alkyl group.

[0018] Y ₁ to Y ₃ are specific examples of the R ₁ to R ₃ and the like. At least one of Y _{1 to} Y ₃ represents an ethenyl group, and is specifically an unsubstituted or alkyl-substituted ethenyl group, preferably a vinyl group or an isopropenyl group. Particularly preferred is a vinyl group. Y ₁ ~
A preferred substitution position for Y ₃ is at the para position of the nitrogen atom.

N represents an integer of 0 to 4, preferably an integer of 0 to 2, and particularly preferably 1. When n is 0, Y ₃ is an alkyl group, an aryl group or an ethenyl group.

Next, specific examples of the compound represented by formula (I) of the present invention are shown below, but the present invention is not limited to these.

[0021]

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[0022]

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[0023]

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[0024]

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Next, a method for synthesizing the compound of the present invention will be described below. Representative synthesis methods are shown in <Synthesis Scheme>.
Benzoazepine used in the present invention is B. Renfroe, C. Harrin
gton, GRRroctor "The Chemistry of Heterocyclic C
ompounds "vol.43, Part1, 1984, John Wiley & Sons I
nc. and HCAxtell et al., J. Org. Chem., 56, 390
6 (1991).

[0026]

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[0027]

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[0028]

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The compound represented by the general formula (I) is purified by silica gel column chromatography and a recrystallization method, and further, if necessary, by a sublimation method.

[0030]

The present invention will be described below with reference to examples.
The present invention is not limited by these examples.

Example 1 (Synthesis of Exemplified Compound (1)) 5H-dibenz [b, f] azepine, 8.7 g (45 mm
ol), p-iodophenethyl alcohol, 12.4 g
(50 mmol), potassium hydroxide, 2.8 g (50 mmol)
Then, 4.8 g (75 mmol) of copper powder and 20 ml of decalin were mixed, and the mixture was heated and stirred at an external temperature of 200 ° C. for 40 hours under a nitrogen stream. After the temperature of the reaction solution was returned to near room temperature, chloroform was added thereto, and the mixture was filtered through celite to remove insolubles, and the filtrate was concentrated. In order to remove decalin, n-hexane was added to the residue, and the solid was filtered.
A crude product of (4-hydroxyethylphenyl) -5H-dibenz [b, f] azepine (A) was obtained. The crude product was purified by silica gel column chromatography to obtain 4.2 g of (A) (30% yield). Next, (A) was dissolved in 4.0 g (12.8 mmol) of tetrahydrofuran (20 ml), and triethylamine (1.8 ml) was dissolved.
(13.0 mmol) and then 2.5 g (13.0 mmol) of p-toluenesulfonyl chloride were added, and the mixture was stirred at room temperature for 3 hours. After extraction with ethyl acetate, the mixture was dried and concentrated, and the residue was dissolved in tetrahydrofuran. 1.5 g (13.0 mmol) of 95% potassium t-butoxide was added thereto, and the mixture was gradually heated to reflux. After about 1 hour, perform chloroform extraction,
By recrystallizing the residue from tetrahydrofuran / methanol, 2.8 g of Exemplified Compound (1) was obtained (yield: 75%). (NMR spectrum) δ (CDCl ₃ ); 5.3 (1H, d, J = 10.5), 5.8 (1
H, d, J = 17.0), 6.2 (2H, d, J = 8.0), 6.8 (2H, S), 6.9
(1H, dd, J = 10.5,17.0), 7.0 (2H, d, J = 8.0) 7.3 ~ 7.5 (8H, m)

Example 2 (Synthesis of Exemplified Compound (2)) 9H-Tribenz [b, d, f] azepine (J. Org.
m.56, 3906 (1991)), 9.2 g (38 mmo
l), 44.8 g (190 mmol) of dibromobenzene, 5.6 g (100 mmol) of potassium hydroxide, 1.6 g of copper powder
(25 ml) and 50 ml of decalin were mixed and heated and stirred at an external temperature of 200 ° C. for 36 hours under a nitrogen stream. The same post-treatment as in Example 1 was carried out, and the product was purified by silica gel chromatography to obtain 3.8 g of 9- (4-bromophenyl) -9H-tribenz [b, d, f] azepine (B) (yield: 25).
%). Next, 3.0 g of (B) (7.
(5 mmol) was dissolved in 20 ml of tetrahydrofuran, and 41 mg (0.075 mmol) of (1,3-bisdiphenylphosphinopropane) dichloronickel was added thereto, followed by stirring at 0 ° C. under a nitrogen stream. 9.0 ml of a 1.0 M solution of vinylmagnesium bromide in tetrahydrofuran (9.0 ml) was added.
mmol) was added by syringe. After stirring for about 2 hours, water was added to the reaction solution, extracted with chloroform, post-treated and concentrated, and the product was purified by silica gel column chromatography to obtain 1.9 g of Exemplified Compound (2) (yield 74%). ). (NMR spectrum) δ (CDCl ₃ ); 5.5 (1H, d, J = 10.2), 5.9 (1
H, d, J = 17.2), 6.4 (2H, d, J = 8.0), 6.9 (1H, dd, J = 10.2,
17.2), 7.0 (2H, d, J = 8.0), 7.4 to 7.8 (12H, m)

[0033]

The polymer derived from the benzazepine compound having an ethenyl group of the present invention has a higher carrier transporting ability than PVK, which is a polymer derived from N-vinylcarbazole, and is suitable for electrophotography and organic electroluminescence devices. It was found that when used, it contributes to higher sensitivity and higher brightness. As a result, a new means for greatly improving their performance has been provided.

Claims (1)

[Claims] 1. A benzazepine derivative represented by the general formula (I). Embedded image (Wherein (A) represents a vinylene or o-arylene group; at least one of Y ₁ , Y ₂ and Y ₃ represents an ethenyl group, and R ₁ , R ₂ , R ₃ , Y ₁ and Y ₂ And Y
₃ represents a hydrogen atom or a substitutable group. Where n is 0
Represents an integer of 1 to 4. When n is 0, Y ₃ is an alkyl group, an aryl group or an ethenyl group. )