JPH09104679A - Oxadiazole derivative and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an oxadiazole derivative which has high emission intensity, good electron transportation and stabilized film-forming properties and is useful as a constituent for organic EL elements and as a fluorescent brightener. SOLUTION: The objective oxadiazole derivative of formula I (A is independently to one another a substituted or unsubstituted alkyl such as methyl or ethyl, a substituted or unsubstituted aryl such as phenyl or biphenyl, a substituted or unsubstituted heterocyclic aromatic ring group such as pyridyl or pyrimidyl) is prepared by, for example, reaction of a compound of formula II (X is a halogen) with a compound of formula III.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a novel oxadiazole derivative and a method for producing the same, and more particularly to a compound useful as an organic EL device or a fluorescent whitening agent and a method for producing the same.

[0002]

2. Description of the Related Art Various oxadiazole derivatives have been known so far, and these are effectively used as a light emitting component or an electron transporting component of an organic EL device.
For example, JP-A-3-205479 discloses an EL device using an oxadiazole derivative having an alkenyl group, a carbazolyl group or an aminophenyl group as a substituent as a light emitting component. However,
These oxadiazole derivatives have problems in emission brightness, electron transporting property and film forming property in a thin film.

[0003]

DISCLOSURE OF THE INVENTION The present invention has a novel oxadiazole derivative having high emission brightness, good electron transporting property and stable film forming property in a thin film, which is useful as a constituent component of an organic EL device. It is an object to provide a manufacturing method thereof.

[0004]

Means for Solving the Problems As a result of intensive studies for achieving the above object, the present inventors have found that an oxadiazole derivative having a certain specific structure is effective, and completed the present invention. I arrived. That is, according to the present invention, the following general formula (A)

Embedded image (In the formula, A independently represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic aromatic ring group.) Provided. According to the invention, the following general formula (B)

Embedded image (However, A is the same as above, X represents a halogen atom), and the following general formula (C)

Embedded image There is provided a method for producing an oxadiazole derivative, which comprises reacting with a compound represented by the formula (A is the same as above) to produce the compound represented by the general formula (A). Furthermore, according to the present invention, the following general formula (D)

Embedded image A compound represented by ACOX (D) (where A and X are the same as above) and the following general formula (E)

Embedded image There is provided a method for producing an oxadiazole derivative, which comprises reacting with a compound represented by the formula (A is the same as above) to produce the compound represented by the general formula (A). According to the invention, the following formula (F)

Embedded image (Where A is the same as above) and the following general formula (D)

Embedded image The compound represented by ACOX (D) (wherein A and X are the same as above) is reacted to give the compound represented by the following general formula (G):

Embedded image (Wherein A is the same as above), and then a dehydration reaction is carried out to produce the compound represented by the general formula (A). A method of manufacturing the same is provided. Furthermore, according to the present invention, the following general formula (B)

Embedded image (Wherein A and X are the same as above) and the following general formula (H)

Embedded image A-CONHNH ₂ (H) (where A is the same as above) is reacted to give a compound represented by the following general formula (G):

Embedded image (Wherein A is the same as above), and then a dehydration reaction is carried out to produce the compound represented by the general formula (A). A method of manufacturing the same is provided.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The following general formula (A) of the present invention

Embedded image In the oxadiazole derivative represented by, A is an alkyl group such as a methyl group, an ethyl group, an n-propyl group or a tert-butyl group, and an aryl group is
Examples thereof include a phenyl group, a biphenyl group, a naphthyl group, a phenanthryl group, a fluorenyl group, an indenyl group, a pyrenyl group and a styryl group.

Further, examples of the heterocyclic aromatic ring group include the following groups. Pyridyl group, pyrimidyl group, pyrazinyl group, triazinyl group, furanyl group, pyrrolyl group, thiophenyl group, quinolyl group, coumarinyl group, benzofuranyl group, benzimidazolyl group, benzoxazolyl group, dibenzofuranyl group, benzothiophenyl group, Indolyl group, carbazolyl group, pyrazolyl group, imidazolyl group, oxazolyl group, isoxazolyl group, thiazolyl group, indazolyl group, benzothiazolyl group, pyridazinyl group, cinnolyl group, quinazolyl group, quinoxalyl group, oxadiazolyl group and the like.

The above-mentioned alkyl group, aryl group and heterocyclic group
Examples of the substituent of the aromatic ring group include the following.
You. (1) Halogen atom, hydroxyl group, trifluoromethyl group,
Cyano group, nitro group. (2) Alkyl group; preferably C₁~ C₆Especially C₁
~ C_FourIs a linear or branched alkyl group. (3) Aryl group (here, carbocyclic and heterocyclic aromatic groups)
Aromatic groups are collectively referred to as aryl groups); phenyl groups,
Futyl, anthryl, acenaphthenyl, fluore
Nyl group, phenanthryl group, indenyl group, pyrenyl
Group, pyridyl group, pyrimidyl group, furanyl group, pyronyl
Group, thiophenyl group, quinolyl group, benzofuranyl group,
Benzothiophenyl group, indolyl group, carbazolyl
Group, benzoxazolyl group, quinoxalyl group, benzoi
Midazolyl group, pyrazolyl group, dibenzofuranyl group, di
A benzothiophenyl group, etc.
Halogen atom, hydroxyl group, cyano group, nitro group,
Even if it is substituted with a kill group, an alkoxy group, an amino group, etc.
Good. (4) Alkoxy group (-OR₁); R₁Is defined in (2)
Represents an alkyl group. (5) Aryloxy group; an aryl group constituting the group
And represents the aryl group defined in (3). (6) Alkylthio group (-SR_Two); R_TwoIs defined in (2)
Represents an alkyl group. Represents an alkyl group or an aryl group as defined in
R such as peridyl group and morpholyl group_ThreeAnd R_FourAnd nitrogen source
You may form a ring with a child. In addition, the urolydyl group
To form a ring in cooperation with a carbon atom on the aryl group
Good. (8) Alkoxycarbonyl group or aryloxycal
Bonyl group (-COOR_Five); R_FiveIs the al defined in (2)
It represents a kill group or an aryl group defined in (3). (9) Acyl group (-COR_Five), A sulfonyl group (-SO_Two
R_Five), A carbamoyl group (-CONR_ThreeR_Four), Or
Sulfamoyl group (-SO_TwoNR_ThreeR_Four): In the formula, R_Three, R
_FourAnd R_FiveIs the meaning defined in (7) and (8) above.
You. Where R_ThreeAnd R_FourOn the carbon on the aryl group
Except when forming a ring together with an atom. (10) such as methylenedioxy group or methylenedithio group
An alkylenedioxy group or an alkylenedithio group. (11) Styryl group represented by the following general formula

Embedded image In the formula, R ₅ represents a substituent defined in (8).

The oxadiazole derivative represented by the general formula (A) of the present invention can be produced by the following method. That is, the following general formula (B)

Embedded image (Wherein A and X are the same as above) and the following general formula (C)

Embedded image (However, A is the same as the above), it is possible to produce the oxadiazole derivative represented by the general formula (A).

As another method, the following general formula (D)

Embedded image A compound represented by ACOX (D) (where A and X are the same as defined above) and the following general formula (E)

Embedded image (However, A is the same as the above), and the compound of the oxadiazole derivative represented by the said general formula (A) can be manufactured by making it react.

As another method, the following general formula (F)

Embedded image (However, A is the same as the above) and the compound represented by the general formula (D) is reacted to give the following general formula (G).

Embedded image (Where A is the same as above) (step A-1), and then dehydration reaction is performed (step B-1) to give the oxa compound represented by the general formula (A). Diazole derivatives can be prepared.

As another method, the compound represented by the general formula (B) and the following general formula (H)

Embedded image A compound represented by the general formula (G) is produced by reacting with a compound represented by A-CONHNH ₂ (H) (where A is the same as above) (step A-2 ), And then dehydration reaction (step B-2) to produce a compound of the oxadiazole derivative represented by the general formula (A).

The starting tetrazole compound represented by the general formula (C) used here is produced by a conventionally known method. For example, Synthesis 71 (1973)
Can be synthesized by the method described in. Further, the reaction between the raw material compound represented by the general formula (B) and the raw material compound represented by the general formula (C), and the raw material compound represented by the general formula (D) and The reaction with the raw material compound represented by the general formula (E) is described in R. D. It is performed according to the oxadiazole synthesis method of Huisgen et al. For example, Ange
w. Chem. , 72, 366 (1060), Che
m. Ber. , 93, 2106 (1960), Tetr
ahedron, 11, 241 (1960), Che
m. Ber. , 98, 2966 (1965).

The tetrazole compound represented by the general formula (E) has the following general formula (I):

Embedded image (However, A is the same as the above), it is manufactured by tetrazole conversion using a compound as a raw material. This method is similar to that described above, for example, in Synthesis (19).
The method described in 73) is applied. Furthermore, the tetrazole compound represented by the general formula (E) has the following general formula (J):

Embedded image (However, A is the same as the above), it is manufactured by tetrazole conversion using a compound as a raw material. As the method, for example, the method described in JP-A-4-234856 is applied.

The compound represented by the general formula (F) used as a starting material is represented by the following general formula (K)

Embedded image (However, A is the same as above, and R represents an alkyl group.) It can be easily produced by reacting an ester derivative represented by hydrazine.

Further, the compound represented by the general formula (B) used as a starting material is obtained by converting the corresponding carboxylic acid into
It can be easily produced by treating with a halogenating agent such as thionyl chloride. The compound represented by the general formula (H) is a known compound and can be easily obtained.

The step (A-1) or (A-2) is usually carried out in the presence of a basic catalyst. As the basic catalyst,
Pyridine and its derivatives, organic bases such as triethylamine, tributylamine, triethanolamine, quinoline, piperazine and morpholine, and inorganic bases such as sodium hydroxide, potassium hydroxide and sodium carbonate, but particularly organic basic catalysts Is preferred.

As the reaction solvent, any solvent can be used as long as it can dissolve the compound represented by the general formula (G), but alcohol solvents such as ethanol and butanol, dioxane and tetrahydrofuran can be used. Ethereal solvent, benzene, toluene, chlorobenzene,
Aromatic solvents such as nitrobenzene, N, N-dimethylformamide, dimethyl sulfoxide and the like are preferable. Further, the above-mentioned organic basic catalyst such as pyridine may be used in excess and used as a solvent. The reaction is usually from room temperature to 150 ° C
Then, it will be completed in a few minutes to a few hours.

In the step (B-1) or the step (B-2) of dehydration reaction, dehydration ring closure by a dehydrating agent such as phosphorus oxychloride, thionyl chloride, polyphosphoric acid, boric acid or toluenesulfonic acid The oxadiazole derivative of (A) is obtained. As the reaction solvent at this time, the solvents shown in the steps (A-1) and (A-2) can be used,
Aromatic solvents such as chlorobenzene, dichlorobenzene, xylene and nitrobenzene, and halogen solvents such as dichloroethane and trichloroethane are particularly preferable.

The amount of the dehydrating agent to be used is appropriately about 1 mol to 10 mol per 1 mol of the compound represented by the general formula (G). For example, phosphorus oxychloride is used in a large excess and the solvent is used. Is also good. The reaction is usually completed at several minutes to 10 hours at 50 to 300 ° C.

Table 1 shows specific examples of the oxadiazole derivative represented by the general formula (A) according to the present invention.

[0021]

[Table 1- (1)]

[0022]

[Table 1- (2)]

[0023]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be specifically described below based on embodiments. Example 1 Acid chloride derivative (L) (general formula (B): X = Cl)
Synthesis of

Embedded image 2.92 gr (0.1 × 1.2 mol) of magnesium and 50 ml of ether were put into a sufficiently dried container while flowing an argon gas. The magnesium pieces were vigorously stirred with a stir bar to expose a fresh surface of magnesium. Stop stirring and add a small amount of 5-Bromo-m-xyl.
ene (in ether solution) was charged. About 0.2 cc of CH ₃ l was added, and the vicinity of CH ₃ l dropping was heated with a dryer. After confirming the start of the reaction, stirring was restarted, and 5-Bromo-m-xylene (1 was dissolved in 50 ml of ether.
8.51 gr) was added dropwise over 75 minutes. At this time, the reaction temperature was kept at 10 ° C. or lower by an ice water bath.
Furthermore, the reaction was performed for 3 hours. At this time, the reaction solution is pa
The color changed from le green to dark green. After forming the Grignard reagent, triphenylphosphine nickel chloride (NiCl ₂ 2Ph ₃ P) was added to
Add mg (0.0002 mol) and add 30 ml
Brmobenzene (14.
92 gr) was added dropwise, and the mixture was reacted at 38-40 ° C for 14 hours. After completion of the reaction, hydrolyze with dilute hydrochloric acid in ice bath, extract with 200 ml of ether, then water (300 ml)
It was washed 3 times with and dried over magnesium sulfate overnight. After the ether was distilled off, column chromatography (Tol / n-Hex)
= 1:10) to obtain 8.88 gr (48.6% yield) of a colorless liquid of the following compound (M).

Embedded image Then, the compound (M) was added at 8.19 gr (0.045 m
ol), H ₂ O (250 ml), KMnO ₄ 28.44 g
r (0.18 mol), NaOH aq. 20 ml (2
N) was put into the flask and heated under reflux for 3 hours. However, since separation of the organic layer was observed, pyridine (150 m
1) and 14.22 gr (0.09 mol) of KMnO ₄ were added and reacted for 7 hours. After completion of the reaction, the insoluble matter was filtered and washed with 500 ml of warm water. Na ₂ S ₂ O as a cleaning solution
₄ (0.09 mol, 11.19 gr) was added, concentrated hydrochloric acid (about 50 ml) was further added, the precipitate was filtered off, and the precipitate was washed with 50 ml of cold water. Crude yield 11.02 gr
(Yield 101.1%). The obtained crude product was treated with n-Hex
(200 ml) and further heated and refluxed with toluene (300 ml) to dissolve and separate unreacted raw materials. Crude yield 2.59
gr (yield 23.76%). Add this to H ₂ O / DMF (7
0/30 ml) to recrystallize [Chemical Formula 14] (N) 2.33
gr (21.38% yield, melting point> 300 ° C.) was obtained.
The elemental analysis values of the compound (N) are shown in Table 2.

Embedded image

[Table 2] Then, the compound (N) 2.18 gr (0.0009 m)
ol) was placed in a reaction vessel with a nitrogen flow, and thionyl chloride (0.18 mol, 21.41 gr) and DMF (2 dr) were added.
Ops) was added and the reaction was carried out at 90 ° C. in an oil bath for 1.5 hours. After the reaction was completed, thionyl chloride was distilled off under reduced pressure, and the residue was sufficiently dried to obtain 2.50 gr of the target compound (L).
(Yield 99.52%) was obtained.

Example 2 Synthesis of tetrazole derivative (O) (general formula (C): A = p-biphenyl)

Embedded image p-Cyanobiphenyl 20.0 gr (0.11 mol)
And 7.98 gr (0.12 mol) of sodium azide and 6.57 gr (0.12 mol) of ammonium chloride were placed in a reaction vessel, 55 ml of N, N-dimethylformamide was added as a solvent, and the temperature was 100 ° C to 110 ° C for 15 hours. Heated to reflux. After cooling, the reaction product was poured into 500 ml of water, filtered, and washed with 500 ml of water to obtain a crude product of 24.0 gr.
(Yield 96.8%) was obtained. This is dioxane 650m
Recrystallize with l, 9.94 gr (yield 40.1%)
To obtain a white powder. The decomposition point of this compound is 239.5.
The temperature was from ℃ to 240.3 ℃. Infrared absorption spectrum is 3
A broad peak over the 200cm ^-1 ~2500cm ^-1 attributable to N-H stretching vibration of tetrazole was observed, it was confirmed that it was the desired product.

Example 3 Oxadiazole derivative (P) (general formula (A): A = p
-Biphenyl) synthesis

Embedded image Acid chloride derivative (L) 1.12 obtained in Example 1
gr (0.004 mol) and the tetrazole derivative (O) obtained in Example 2 2.67 gr (0.012 mol)
Were placed in a reaction vessel, 50 ml of pyridine (dehydrated calcium hydride) was added as a solvent, and the mixture was heated under reflux for 13 hours.
After allowing to cool, the reaction product was poured into 1000 ml of water for sufficient precipitation and then filtered to obtain 2.34 gr of a crude product (yield 98.3).
%). This was subjected to column chromatography (developing solvent chloroform: tetrahydrofuran = 30: 1 (v
The product was purified by an aluminum ratio)) and recrystallized with 59 ml of toluene to obtain 255 mgr (yield 10.7%) of white needles. Melting point: 268.0-286.5 ° C An infrared absorption spectrum (KBr tablet method) is shown in Fig. 1. Elemental analysis value

[Table 3] From the above, it was confirmed that the target product was obtained.

Example 4 1.12 gr of the acid chloride derivative obtained in Example 1
(0.004 mol) and 2.35 gr (0.012 mol) of the tetrazole derivative (Q) shown below were placed in a reaction vessel, and pyridine (calcium hydride dehydration) was used as a solvent.
50 ml was added and the mixture was heated under reflux for 13 hours. 100 after cooling
The reaction product was poured into 0 ml of water to cause sufficient precipitation, and then filtered. Column chromatography (developing solvent chloroform: tetrahydrofuran = 30: 1 (volu
column chromatography with methylene chloride. Recrystallization with 45 ml of toluene gave the oxadiazole derivative (R) shown below.
(General formula (A): A = α-naphthyl) white needle-like material 40
0 mgr was obtained. Melting point: 251.0-252.0 ° C. The infrared absorption spectrum (KBr tablet method) is shown in FIG. Elemental analysis value

[Table 4]

Embedded image

Embedded image

Application Example 1 (Application of organic EL element to electron injecting and transporting material) ITO (indium tin oxide: film thickness: 200) thoroughly ultrasonically cleaned with a neutral detergent and isopropyl alcohol
0 Å) 400 Å of the following compound (S) as a hole injecting and transporting layer and 1 of the following compound (T) as a light emitting layer on a substrate
50 Å, 150 Å of the oxadiazole derivative (P) as an electron injecting and transporting layer, and 300 Å of the following compound (U) as a second electron injecting and transporting layer were sequentially formed by vacuum vapor deposition. Further, a mask is set on the substrate, and Mg: Ag =
2,000 liters of 10: 1 (vapor deposition rate) cathode is formed and 2 m
An m × 2 mm square EL device was prepared. The degree of vacuum during vapor deposition was 0.7 × 10 ⁻⁷ torr, and the substrate temperature was room temperature. When a DC voltage was applied to the EL element thus produced through a lead wire, the current density was 30 mA / cm.
^{At 2} , the emission luminance of 248 cd / m ² was observed. The applied voltage at this time was 7.24V. The EL light emission peak was 468 nm, and blue light emission from the light emitting layer was observed. Since the EL emission coincides with the fluorescent component of the light emitting layer, the oxadiazole derivative (P) forming the electron injecting and transporting layer injects electrons into the light emitting layer, and conversely does not accept hole injection from the light emitting layer. It can be seen that the oxadiazole derivative (P) has an electron transporting ability and a hole blocking effect.

Application Example 2 (Application of an organic EL device to an electron injecting and transporting material) ITO (indium tin oxide: film thickness: 200) which was sequentially cleaned by ultrasonic cleaning with a neutral detergent and isopropyl alcohol.
0 Å) 400 Å of the following compound (S) as a hole injecting and transporting layer and 1 of the following compound (T) as a light emitting layer on a substrate
50 Å, 150 Å of the oxadiazole derivative (R) as an electron injecting and transporting layer, and 300 Å of the following compound (U) as a second electron injecting and transporting layer were sequentially formed by vacuum vapor deposition. Further, a mask is set on the substrate, and Mg: Ag =
2,000 liters of 10: 1 (vapor deposition rate) cathode is formed and 2 m
An m × 2 mm square EL device was prepared. The degree of vacuum during vapor deposition was 0.7 × 10 ⁻⁷ torr, and the substrate temperature was room temperature. When a DC voltage was applied to the EL element thus produced through a lead wire, the current density was 30 mA / cm ²
In the emission luminance of 382 cd / m ² was observed. The applied voltage at this time was 6.2V. The EL light emission peak was 475 nm, and blue light emission from the light emitting layer was observed. Since the EL emission coincides with the fluorescent component of the light emitting layer, the oxadiazole derivative (R) forming the electron injecting and transporting layer injects electrons into the light emitting layer, and conversely does not accept hole injection from the light emitting layer. It can be seen that the oxadiazole derivative (R) has an electron transporting ability and a hole blocking effect. Also, the E created in this way
When the L element was left for 30 days at room temperature and then driven again, no remarkable deterioration was observed.

[0029]

Embedded image

Embedded image

Embedded image

[0030]

INDUSTRIAL APPLICABILITY The novel oxadiazole derivative represented by the general formula (A) according to the present invention exhibits high luminous efficiency in an organic EL device and forms a stable glass state in a thin film for a long period of time. By doing so, it is useful as a constituent component of an EL element. Further, the present invention can provide a method for producing the novel oxadiazole derivative.

[Brief description of the drawings]

FIG. 1 is an infrared absorption spectrum diagram (KBr tablet method) of an oxadiazole derivative (P) according to the present invention.

FIG. 2 is an infrared absorption spectrum diagram (KBr tablet method) of an oxazoazole derivative (R) according to the present invention.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display area C07D 413/14 333 C07D 413/14 333 // C09B 57/00 C09B 57/00 Y C09K 11/06 9280-4H C09K 11/06 Z H05B 33/14 H05B 33/14

Claims (5)

[Claims] 1. The following general formula (A): (In the formula, each A independently represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic aromatic ring group). 2. The following general formula (B): (In the formula, each A independently represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic aromatic ring group, and X represents a halogen atom.) Compound represented by the following general formula (C): The method for producing an oxadiazole derivative according to claim 1, wherein the compound represented by the general formula (A) is produced by reacting with a compound represented by the formula (A is the same as above). . 3. The following general formula (D): embedded image ACOX (D) (wherein A is independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryl group) Represents a heterocyclic aromatic ring group, X represents a halogen atom), and a compound represented by the following general formula (E): The method for producing an oxadiazole derivative according to claim 1, wherein the compound represented by the general formula (A) is produced by reacting with a compound represented by the formula (A is the same as above). . 4. The following formula (F): (Wherein each A independently represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic aromatic ring group), and a compound represented by the following general formula: Formula (D) embedded image ACOX (D) (In the formula, A is the same as above. X represents a halogen atom.)
A compound represented by the following general formula (G): The compound represented by the general formula (A) is produced by producing a compound represented by the formula (A is the same as above) and then performing a dehydration reaction. Of the oxadiazole derivative of 1. 5. The following general formula (B): (In the formula, each A independently represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic aromatic ring group, and X represents a halogen atom.) And a compound represented by the following general formula (H): A-CONHNH ₂ (H) (where A is the same as above), and the following general formula (G) 7] The compound represented by the general formula (A) is produced by producing a compound represented by the formula (A is the same as above) and then performing a dehydration reaction. Of the oxadiazole derivative of 1.