JP2003040815A - Hydrocarbon compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a new hydrocarbon compound suitable for a functional material, for example, a fluorescent material for an organic electroluminescent element. SOLUTION: This compound is expressed by general formula (1). [X1 to X16 are each independently H, a halogen atom, a linear, a branched or a cyclic alkyl group, a linear, a branched or a cyclic alkoxy group or a (substituted) aryl group, and each neighboring group selected from the X1 to X16 may mutually bonds each other with the substituting carbon atoms to form a (substituted) aliphatic carbon ring, (with the proviso that all of the each X1 to X16 is not H at the same time)].

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] The present invention relates to a novel hydrocarbon compound.
About the compound. [0002] 2. Description of the Related Art Conventionally, hydrocarbon compounds have been well known.
Have been. Recently, important constituent compounds of various functional materials have been
As an object, it is attracting attention. For example, recently
Organic electroluminescent device (organic element) using organic material for optical material
Electron emission device) has been developed.
(Appl. Phys. Lett.,51, 913 (1987)]. Organic electric field
The light-emitting element consists of a thin film containing a fluorescent organic compound,
It has a structure sandwiched between the poles, and the thin film has electrons and holes
(Holes) are injected and recombined to form excitons
(Exciton), and when this exciton is deactivated,
An element that emits light using emitted light. Organic electric field
The light emitting element emits light at a low DC voltage of about several volts to several tens of volts.
Is possible and select the type of fluorescent organic compound
By various colors (for example, red, blue, green)
Light emission is possible. Organic electric field generator with such features
Optical devices are expected to be applied to various light emitting devices, display devices, etc.
Have been. For this organic electroluminescent device, for example, light emitting
It has been proposed to use hydrocarbon compounds as materials.
You. For example, anthracene derivatives (for example, see
-294197, JP-A-11-323323
Report), fluoranthene derivatives (Japanese Patent Application Laid-Open No. 10-18924)
No. 8), a benzofluoranthene derivative (Japanese Unexamined Patent Publication No.
Publication No. 189247) discloses light emission for an organic electroluminescent device.
It has been proposed for use as a material. Organic electroluminescence
Light emitting materials for devices include various colors (for example, blue,
(Green, red)
Various compounds are required for this purpose. Related to the present invention
Benzo [ghi] diindeno [1,2,3-cd: 1 ', 2', 3'-l'm '] peri
Unsubstituted benzo [ghi] diindeno
[1,2,3-cd: 1 ', 2', 3'-l'm '] perylene is known [eg
For example, Chem. Ber.,95, 673 (1962), J. Photochem. Pho
tobiol. A. Chem., 69, 27 (1992).
]. However, no derivative of the compound is known. [0003] The object of the present invention is to provide a novel
To provide a stable hydrocarbon compound. Further details
For example, for example, as a light emitting material for an organic electroluminescent element,
Provide a hydrocarbon compound that can be suitably used
That is. [0004] Means for Solving the Problems The present inventors have proposed various kinds of charcoal.
Hydrogen compounds, especially light-emitting materials for organic electroluminescent devices
Diligent study on hydrocarbon compounds that can be suitably used
As a result, the present invention has been completed. That is, the present invention
Refers to a compound represented by the general formula (1)
You. Embedded image [Where X₁~ X₁₆Are each independently a hydrogen atom, halo
Gen atom, straight chain, branched or cyclic alkyl group, straight chain,
A branched or cyclic alkoxy group, or substituted or unsubstituted
Represents a substituted aryl group;₁~ X₁₆Choose from
Adjacent groups are bonded to each other and
Substituted or unsubstituted carbocyclic aliphatic
May form a ring (provided that X is₁~ X₁₆At the same time
(It does not represent a hydrogen atom.)] [0005] BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
I do. The hydrocarbon compound of the present invention is represented by the general formula (1).
Hydrocarbon compounds. Embedded image [Where X₁~ X₁₆Are each independently a hydrogen atom, halo
Gen atom, straight chain, branched or cyclic alkyl group, straight chain,
A branched or cyclic alkoxy group, or substituted or unsubstituted
Represents a substituted aryl group;₁~ X₁₆Choose from
Adjacent groups are bonded to each other and
Substituted or unsubstituted carbocyclic aliphatic
May form a ring (provided that X is₁~ X₁₆At the same time
(It does not represent a hydrogen atom.)] In the compound represented by the general formula (1),
X₁~ X₁₆Are each independently a hydrogen atom or a halogen atom
Straight-chain, branched or cyclic alkyl, straight-chain, branched or
Or a cyclic alkoxy group, or a substituted or unsubstituted
Represents an aryl group; ₁~ X₁₆Chosen from
Adjacent groups are bonded to each other to form a carbon
Forms a substituted or unsubstituted carbocyclic aliphatic ring with atoms
It may be composed. Where X₁~ X₁₆At the same time
It does not represent a hydrogen atom. [0007] In the present invention, the aryl group is
For example, carbocyclic aromatic groups such as phenyl group and naphthyl group
Groups such as furyl, thienyl, pyridyl, etc.
Represents a heterocyclic aromatic group, preferably a carbocyclic aromatic group
Represents a group. In the compound represented by the general formula (1),
More preferably, X₁~ X₁₆Is a hydrogen atom, a halogen atom
, Linear, branched or cyclic alkyl having 1 to 24 carbon atoms
Group, linear, branched or cyclic alkoxy having 1 to 24 carbon atoms
Or a substituted or unsubstituted group having 4 to 24 carbon atoms.
Represents a reel group, more preferably a hydrogen atom,
Atom, linear, branched or cyclic alkyl having 1 to 14 carbon atoms
A kill group, a linear, branched or cyclic alkyl group having 1 to 14 carbon atoms.
Coxy group, or substituted or unsubstituted C6-C24
Represents an aryl group. In the general formula (1), X₁~ X₁₆Utensils
Examples of the body include, for example, a hydrogen atom, for example, a fluorine atom.
Atom, chlorine atom, halogen atom such as bromine atom, for example,
Methyl group, ethyl group, n-propyl group, isopropyl
Group, n-butyl group, isobutyl group, sec-butyl group, te
rt-butyl group, n-pentyl group, isopentyl group, neo
Pentyl group, tert-pentyl group, n-hexyl group, 1-
Methylpentyl group, 4-methyl-2-pentyl group, 3,
3-dimethylbutyl group, 2-ethylbutyl group, n-heptane
Tyl group, 1-methylhexyl group, cyclohexylmethyl
Group, n-octyl group, tert-octyl group, 1-methyl
Butyl group, 2-ethylhexyl group, 2-propyl pent
Group, n-nonyl group, 2,2-dimethylheptyl group,
2,6-dimethyl-4-heptyl group, 3,5,5-tri
Methylhexyl group, n-decyl group, n-undecyl group,
1-methyldecyl group, n-dodecyl group, n-tridecyl
Group, 1-hexylheptyl group, n-tetradecyl group, n
-Pentadecyl group, n-hexadecyl group, n-heptade
A sil group, n-octadecyl group, n-eicosyl group, n-
Tricosyl group, n-tetracosyl group, cyclopentyl
Group, cyclohexyl group, 4-methylcyclohexyl group,
4-tert-butylcyclohexyl group, cycloheptyl
Group, cyclooctyl group, etc.
Ruquil group, For example, methoxy, ethoxy, n-propyl
Loxy, isopropoxy, n-butoxy, iso
Butoxy group, sec-butoxy group, n-pentyloxy
Group, neopentyloxy group, cyclopentyloxy group,
n-hexyloxy group, 3,3-dimethylbutyloxy
Group, 2-ethylbutyloxy group, cyclohexyloxy
Group, n-heptyloxy group, n-octyloxy group, 2
-Ethylhexyloxy group, n-nonyloxy group, n-
Decyloxy group, n-undecyloxy group, n-dodecy
Loxy group, n-tridecyloxy group, n-tetradeci
Loxy group, n-pentadecyloxy group, n-hexade
Siloxy group, n-heptadecyloxy group, n-octa
Decyloxy group, n-eicosyloxy group, n-trico
Straight chain such as siloxy group, n-tetracosyloxy group,
A branched or cyclic alkoxy group, For example, a phenyl group, 2-methylphenyl
Group, 3-methylphenyl group, 4-methylphenyl group, 3
-Ethylphenyl group, 4-ethylphenyl group, 4-n-
Propylphenyl group, 4-isopropylphenyl group, 4
-N-butylphenyl group, 4-isobutylphenyl group,
4-tert-butylphenyl group, 4-n-pentylphenyi
Group, 4-isopentylphenyl group, 4-tert-pentyl
Phenyl group, 4-n-hexylphenyl group, 4-cycl
Rohexylphenyl group, 4-n-heptylphenyl group,
4-n-octylphenyl group, 4-n-nonylphenyl
Group, 4-n-decylphenyl group, 4-n-undecylph
Phenyl, 4-n-dodecylphenyl, 4-n-tetra
Ladecylphenyl group, 4-n-hexadecylphenyl
Group, 4-n-octadecylphenyl group, 2,3-dimethyl
Phenyl group, 2,4-dimethylphenyl group, 2,5-
Dimethylphenyl group, 2,6-dimethylphenyl group,
3,4-dimethylphenyl group, 3,5-dimethylphenyl
Group, 3,4,5-trimethylphenyl group, 2,3
5,6-tetramethylphenyl group, 5-indanyl group,
1,2,3,4-tetrahydro-5-naphthyl group, 1,
2,3,4-tetrahydro-6-naphthyl group, 2-metho
Xyphenyl group, 3-methoxyphenyl group, 4-methoxy
Cyphenyl group, 3-ethoxyphenyl group, 4-ethoxy
Phenyl group, 4-n-propoxyphenyl group, 4-iso
Propoxyphenyl group, 4-n-butoxyphenyl group,
4-isobutoxyphenyl group, 4-n-pentyloxy
Phenyl group, 4-n-hexyloxyphenyl group, 4-
Cyclohexyloxyphenyl group, 4-n-heptyl
A xyphenyl group, a 4-n-octyloxyphenyl group,
4-n-nonyloxyphenyl group, 4-n-decyloxy
A cyphenyl group, a 4-n-undecyloxyphenyl group,
4-n-dodecyloxyphenyl group, 4-n-tetrade
Siloxyphenyl group, 4-n-hexadecyloxyf
Enyl group, 4-n-octadecyloxyphenyl group, 2,3-dimethoxyphenyl group, 2,4-
Dimethoxyphenyl group, 2,5-dimethoxyphenyl
Group, 3,4-dimethoxyphenyl group, 3,5-dimethoxy
Cyphenyl group, 3,5-diethoxyphenyl group, 2-meth
Toxic-4-methylphenyl group, 2-methoxy-5-methyl
Tylphenyl group, 3-methoxy-4-methylphenyl
Group, 2-methyl-4-methoxyphenyl group, 3-methyl
-4-methoxyphenyl group, 3-methyl-5-methoxy
Phenyl group, 2-fluorophenyl group, 3-fluorophenyl
Phenyl, 4-fluorophenyl, 2-chlorophenyl
Group, 3-chlorophenyl group, 4-chlorophenyl group,
4-bromophenyl group, 4-trifluoromethylphenyi
Group, 2,4-difluorophenyl group, 2,4-dichloro
Rophenyl group, 3,4-dichlorophenyl group, 3,5-
Dichlorophenyl group, 2-methyl-4-chlorophenyl
Group, 2-chloro-4-methylphenyl group, 3-chloro-
4-methylphenyl group, 2-chloro-4-methoxyphen
Nyl group, 3-methoxy-4-fluorophenyl group, 3-
Methoxy-4-chlorophenyl group, 3-fluoro-4-
Methoxyphenyl group, 4-phenylphenyl group, 3-f
Phenylphenyl group, 2-phenylphenyl group, 4-
(4'-methylphenyl) phenyl group, 4- (4'-meth
Toxylphenyl) phenyl group, 1-naphthyl group, 2-na
Phthyl group, 4-methyl-1-naphthyl group, 4-ethoxy
-1-naphthyl group, 6-n-butyl-2-naphthyl group,
6-methoxy-2-naphthyl group, 7-ethoxy-2-na
Fthyl group, 2-furyl group, 2-thienyl group, 3-thienyl
Group, 2-pyridyl group, 3-pyridyl group, 4-pyridyl
And substituted or unsubstituted aryl groups such as
And more preferably a hydrogen atom, a fluorine atom, a chlorine atom.
, Linear, branched or cyclic alkyl having 1 to 20 carbon atoms
Group, linear, branched or cyclic alkoxy having 1 to 20 carbon atoms
Or a substituted or unsubstituted group having 6 to 20 carbon atoms.
A reel group, more preferably a hydrogen atom, fluorine
Atom, chlorine atom, C1-C16 linear, branched or ring
Alkyl group, straight-chain, branched or cyclic having 1 to 16 carbon atoms
Alkoxy group, or C6-C20 substituted or
Is an unsubstituted aryl group, particularly preferably a hydrogen atom
Atom, fluorine atom, chlorine atom, straight chain having 1 to 14 carbon atoms,
A branched or cyclic alkyl group, a straight chain having 1 to 14 carbon atoms,
A branched or cyclic alkoxy group or 6 to 20 carbon atoms
Is a substituted or unsubstituted aryl group. Furthermore, X₁
~ X₁₆Groups adjacent to each other are bonded to each other and
Substituted or unsubstituted carbocyclic ring with the carbon atom being replaced
May form a formula aliphatic ring;
Form a substituted or unsubstituted carbocyclic aliphatic ring of Formulas 4 to 10
May be formed. In the general formula (1), X₆And X₇But
X is a hydrogen atom, and other X is a hydrogen atom, having 1 carbon atom
Up to 16 linear, branched or cyclic alkyl groups, or
A substituted or unsubstituted aryl group having 6 to 20 carbon atoms
Compounds are more preferred. Where X₁~ X₁₆Is water at the same time
It does not represent an elementary atom. Carbonization represented by the general formula (1)
Hydrogen compounds are, for example, light-emitting materials for organic electroluminescent devices.
For high brightness and durability
To provide an organic electroluminescent device emitting yellow-green light.
It becomes possible. In addition, hydrocarbon conversion represented by the general formula (1)
The compound is an unsubstituted benzo [gh] related compound of the present invention.
i] diindeno [1,2,3-cd: 1 ', 2', 3'-l'm '] from perylene
Also, as a light emitting material for organic electroluminescent elements, with high efficiency,
It is a material that emits light with high luminance. The hydrocarbon represented by the general formula (1) of the present invention
Specific examples of the compound include, for example, the following compounds
However, the present invention is not limited to these.
There is no. [0014] Embedded image[0015] Embedded image[0016] Embedded image[0017] Embedded image[0018] Embedded image[0019] Embedded image[0020] Embedded image[0021] Embedded image[0022] Embedded image[0023] Embedded image[0024] Embedded image[0025] Embedded image[0026] Embedded image[0027] Embedded image[0028] Embedded image[0029] Embedded image[0030] Embedded image[0031] Embedded image[0032] Embedded image[0033] Embedded image[0034] Embedded image[0035] Embedded image[0036] Embedded image[0037] Embedded image[0038] Embedded image[0039] Embedded image[0040] Embedded image[0041] Embedded image[0042] Embedded imageA hydrocarbon compound represented by the general formula (1)
Is a method known per se (for example, Chem. Ber.,95, 67
3 (1962), Helv. Chim. Acta,42, 235 (1959), Chem.
Ber.,119, 2373 (1986), J. Chem. Soc., 1555 (194
9)).
That is, for example, the compound represented by the general formula (2)
After reacting the compound represented by the general formula (3), for example,
The compound is dehydrogenated by the action of chloranil, and represented by the general formula (4).
After preparing the compound to be prepared, a base (for example, calcium oxide)
, Potassium hydroxide, sodium hydroxide, sodium carbonate
) Can be produced. [0044] Embedded image[X in the above formula₁~ X₁₆Represents the same meaning as in general formula (1).
You] The diindeno represented by the general formula (2)
[1,2,3-cd: 1 ', 2', 3'-l'm '] perylene derivatives are themselves
Known methods [for example, J. Amer. Chem. Soc.,102, 6504
 (1980)).
Wear. That is, the compound represented by the general formula (5)
An oxidizing agent (for example, chloride
Reacted in the presence of diiron, lead tetraacetate, cobalt trifluoride)
Can be manufactured. [0046] Embedded image [X in the above formula₁~ X₅, And X₈~ X₁₆Is the general formula
Represents the same meaning as (1)] The carbonization represented by the general formula (1) of the present invention
The hydrogen compound is optionally used in a solvent (for example, toluene).
Solvates with aromatic hydrocarbon solvents such as ene)
Although it may be manufactured in a mold that has been
And non-solvates. In general formula (1)
A hydrocarbon compound represented by, for example, an organic electroluminescent element
Recrystallization method, column chromatography
Purification methods such as the chromatography method and sublimation purification method, or
Use these methods in combination to use compounds with increased purity.
Is preferred. [0048] The present invention will be described below with reference to Production Examples and Examples.
However, the present invention is, of course, limited to these.
It is not something to be done. Example 1 Production of Compound of Exemplified Compound No. A-5 1,4,9,12-tetramethyldiindeno [1,2,3-cd:
1 ', 2', 3'-lm] Perylene 10g and chloranil 30g anhydrous
The mixture was refluxed with maleic acid (200 g) for 6 hours.
Nitrobenzene (100 g) was added to the reaction mixture.
Then, after cooling to room temperature, the precipitated solid was filtered.
This solid was combined with sodium hydroxide (30 g) with nitrogen
The mixture was stirred at 360 ° C. for 1 hour under an atmosphere. Then the reaction mixture
The mixture was cooled to room temperature and washed with water. Alumina residue
Processed by column chromatography (eluent: toluene)
Was. After the toluene was distilled off under reduced pressure, the residue was
Recrystallized from a mixed solvent of acetone, Exemplified Compound No. A-
1.5 g of compound 5 was obtained as red crystals. Melting point 250 ° C or higher Absorption maximum (in toluene) 478 nm The used 1,4,9,12-tetrame
Tildiindeno [1,2,3-cd: 1 ', 2', 3'-lm] perylene is
It was manufactured by the following method. 7,10-dimethylfluora
30 g of cobalt and 40 g of cobalt trifluoride
The mixture was heated and refluxed in acetic acid (1000 ml) for 30 hours.
After trifluoroacetic acid was distilled off under reduced pressure, water (2
(00 ml), the solid was filtered and washed with water. this
After washing the solid with acetone, alumina column chromatography
It was processed by chromatography (eluent: toluene). toluene
Was distilled off under reduced pressure, and the residue was mixed with toluene and acetone.
Recrystallized from the combined solvent, 1,4,9,12-tetramethyl
Diindeno [1,2,3-cd: 1 ', 2', 3'-lm] perylene
12 g were obtained as crystals. Examples 2 to 27 In Production Example 1, 1,4,9,12-tetramethyldi
Use of indeno [1,2,3-cd: 1 ', 2', 3'-lm] perylene
Instead, various diindeno [1,2,3-cd: 1 ', 2', 3'-lm]
The method described in Example 1 except that the ren derivative was used.
[Ghi] diene represented by various general formulas (1)
Production of indeno [1,2,3-cd: 1 ', 2', 3'-lm] perylene derivative
did. Table 1 shows the diindeno used [1,2,3-cd: 1 ', 2',
3'-lm] perylene derivative and the general formula of the present invention produced
Benzi [ghi] diindeno [1,2,3-cd:
[1 ', 2', 3'-lm] perylene derivatives are indicated by the exemplified compound numbers.
Was. The absorption maximum (nm) in toluene is also shown.
Was. The compound represented by the general formula (1) produced is
It is a red-purple crystal, and the melting point of the compound is 25
It was 0 ° C or higher. [0051] [Table 1] [0052] [Table 2][0053] [Table 3] [0054] [Table 4] [0055] [Table 5][0056] [Table 6] Application Example 1 Application example to an organic electroluminescent device Glass with 200nm thick ITO transparent electrode (anode)
Substrate with a neutral detergent, acetone, and ethanol.
Sonic cleaning was performed. The substrate is dried using nitrogen gas,
After UV / ozone cleaning, the substrate holder of the evaporation system
After fixing to 3 × 10^-6The pressure was reduced to Torr.
First, 4,4 ', 4 "-tris is formed on the ITO transparent electrode.
[N- (3 "'-methylphenyl) -N-phenylamido
[No] triphenylamine at a deposition rate of 0.1 nm / sec.
It was deposited to a thickness of 50 nm to form a first hole injection / transport layer.
Then, 4,4'-bis [N-phenyl-N- (1 "-
Naphthyl) amino] biphenyl and Exemplified Compound No. D-1
From different evaporation sources, a deposition rate of 0.2 nm /
In seconds, co-deposit to a thickness of 20 nm (weight ratio 100: 5)
Then, the light emitting layer also served as the second hole injection / transport layer. Next
In addition, tris (8-quinolinolate) aluminum
At a deposition rate of 0.2 nm / sec to a thickness of 50 nm.
It vapor-deposited and was set as the electron injection transport layer. On top of that, a mug
Nesium and silver are deposited at a deposition rate of 0.2 nm / sec for 200 n
m (thickness ratio: 10: 1) to form a cathode.
An electroluminescent device was fabricated. In addition, evaporation was performed under reduced pressure in the evaporation tank.
The test was performed while maintaining the condition. Organic EL device fabricated
And a DC voltage of 12 V was applied in a dry atmosphere.
Filter, 57mA / cm²Current flowed. Brightness 3100c
d / m²Of yellowish green was observed. Application Examples 2 to 5 In Application Example 1, the compound of Exemplified Compound No. D-1 was used.
Instead of using the compound of Exemplified Compound No. A-5 (Application
Example 2), compound of Exemplified Compound No. B-2 (Application Example 3),
Compound of Exemplified Compound No. D-37 (Application Example 4), Exemplified
Except using the compound of Compound No. D-48 (Application Example 5)
Manufactured an organic electroluminescent device by the method described in Application Example 1.
Made. Apply 12 V direct to each element under dry atmosphere.
Upon application of a flowing voltage, yellow-green light emission was confirmed.
The characteristics were further examined, and the results are shown in Table 2. Application Comparative Example In Application Example 1, the compound of Exemplified Compound No. D-1 was used.
Instead of using benzo [ghi] diindeno [1,2,3-cd:
1 ', 2', 3'-lm]
An organic electroluminescent device was produced by the method described above. Made
When a DC voltage of 12 V was applied to the device in a dry atmosphere
At this time, yellow-green light emission was confirmed. Further adjust its characteristics
In addition, the results are shown in Table 2. [0060] [Table 7] From the application examples 1 and 2 shown in FIG.
Benzo [ghi] diindeno [1,2,3-cd represented by the formula (1):
[1 ', 2', 3'-lm] Perylene derivative using organic electroluminescent device
When used as a material, unsubstituted benzo [ghi] diindeno
[1,2,3-cd: 1 ', 2', 3'-lm]
Thus, it was found that light was emitted with higher efficiency. [0062] According to the present invention, functional materials such as organic
Excellent hydrocarbon compounds as light emitting materials for electroluminescent devices
It became possible to provide.

   ────────────────────────────────────────────────── ─── Continuation of front page    (72) Inventor Tsutomu Ishida             580-32 Nagaura, Sodegaura-shi, Chiba Mitsui Chemicals, Inc.             In the formula company (72) Inventor Yoshimitsu Tanabe             580-32 Nagaura, Sodegaura-shi, Chiba Mitsui Chemicals, Inc.             In the formula company (72) Inventor Yoshiyuki Toya             580-32 Nagaura, Sodegaura-shi, Chiba Mitsui Chemicals, Inc.             In the formula company F term (reference) 4H006 AA01 AB64 EA37 GP03

Claims (1)

Claims: 1. A hydrocarbon compound represented by the general formula (1). Embedded image [Wherein, X _{1 to} X ₁₆ each independently represent a hydrogen atom, a halogen atom, a straight-chain, branched or cyclic alkyl group, a straight-chain,
Represents a branched or cyclic alkoxy group or a substituted or unsubstituted aryl group, and further, adjacent groups selected from X _{1 to} X ₁₆ are bonded to each other to form a substituted or unsubstituted group together with a substituted carbon atom. May form a carbocyclic aliphatic ring (however, X _{1 to} X ₁₆ do not represent a hydrogen atom at the same time)]