JP3030423B2 - Novel olefin compound, method for producing the same, and intermediate thereof - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel olefin compound containing a pyrene ring, a method for producing the same, and an intermediate thereof. More specifically, the present invention relates to an organic electronic material having a molecular structure in which .pi. The present invention relates to a useful and novel olefin compound, a production method thereof, and an intermediate thereof.

[0002]

2. Description of the Related Art Regarding the synthesis of olefin compounds,
"KB Becker; SYNTHESIS 34
1 (1983) ", a number of methods are introduced under the title" Synthesis of Stilbenes ". Regarding the olefin compound containing a pyrene ring, (1) a method by Grignard reaction described in the above-mentioned literature,
(2) Method by Anil synthesis, (3) Knoveve
The following literature discloses synthesis examples using a method by the nagel reaction, (4) a method by the Wittig reaction, (5) a method by the Wittig-Horner reaction, and the like. That is, as an example of (1), “Rec.tra
v. chim. , 74, 1119 (1955) ", a styrylpyrene is obtained with pyrenealdehyde, benzylmagnesium chloride and formic acid, and" C. A. 71, 71927 "includes 1- (2-
Naphthyl) -2- (3-pyrenyl) ethylene is described. Further, as an example of (3), Pyrene-Patent Publication No. 2,513,190 (1975)
A method for obtaining 1- (2,4,6-trinitrostyryl) pyrene by reacting 1-aldehyde with 2,4,6-trinitrotoluene is described. However, these methods (1) to (3) need to be performed under dehydration, require high temperature and long time, and have a problem in reaction operability or reaction, and also have a problem of electron withdrawing. There are difficulties such as being restricted by the compound activated by the group.

On the other hand, W using the phosphorus compound of the above (4)
The ittig reaction is a very excellent method for performing olefin synthesis under mild conditions.
Chem. Soc. Jap. 44, 2231 (1
971) ”and“ 45,875 (1972) ”
The synthesis of olefins using pyrenylmethyltriphenylphosphonium bromide as Wittig reagent is described. However, this reaction generally gives a mixture of cis-trans, and has some drawbacks such as low reactivity with certain ketones and difficulty in removing phosphine oxide which is an equimolar by-product with olefins. That is true. Also, Witt of the above (5)
ig-horner method, that is, pyrenaldehyde and 4
A method for obtaining a substituted aminostyrylpyrene by reaction with diethyl-diphenylaminobenzylphosphonate is disclosed in JP-A-1-252965 and JP-A-1-253753. From the viewpoint of synthetic chemistry, it must be said that the synthesis of acid esters is extremely difficult.

[0004]

As described above, with respect to the production of an olefin compound containing a pyrene ring, any of the conventional methods has some problems, and no satisfactory method has been found yet. In addition, the conventional production method has various restrictions, and at present, the applicable range of the compound that can be synthesized is narrow. Accordingly, an object of the present invention is to provide a novel olefin compound having a molecular structure in which π conjugation is expanded, which is useful as an organic electronic material, and a method for producing an olefin compound which overcomes the problems of the prior art. Another object of the present invention is to provide a novel intermediate for synthesizing these olefin compounds.

[0005]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that in the Wittig-Horner reaction, by using diethyl 1-pyrenylmethylphosphonate, pyrene can be reacted with various carbonyl compounds. The present inventors have found that the synthesis of a novel olefin compound having a ring can be carried out extremely effectively, and have completed the present invention.

That is, according to the present invention, the following general formula
A novel olefin compound represented by (1) is provided.

Embedded image Wherein n is 0 or 1, m is 1, Ar, R ¹ ,
R ² , n and m each represent the following. When n = 0 and m = 1, R ¹ represents a hydrogen atom, Ar represents a methoxynaphthyl group, and when n = 1 and m = 1, R ¹ represents a hydrogen atom, and R ² represents a hydrogen atom or a methyl group. And Ar is a dimethylamino-substituted phenyl group, or methoxy
Represents a substituted phenyl group. )

Further, according to the present invention, the following general formula (2)
And a phosphonic ester derivative represented by the following general formula:
(3) a carbonyl compound represented by the following general formula which comprises reacting in the presence of a basic compound
A method for producing the olefin compound represented by (1) is provided.

Embedded image (In the formula, R ³ represents an alkyl group having 1 to 4 carbon atoms .)

Embedded image (Where n is 0 or 1, m is 1 or 2, R ¹ and R ² are
A hydrogen atom, a methyl group or Ar is a halogen atom as a substituent.
, Cyano group, alkyl group having 1 to 4 carbon atoms, alkoxy
Or —NR ⁵ R ⁶ group (where R ⁵ and R ^{6 each} have 1 carbon atom)
To 4 alkyl groups, an aralkyl group having 1 to 4 carbon atoms,
Is an alkyl group having 1 to 4 carbon atoms as a substituent,
Substituted or unsubstituted aryl having 1 to 4 alkoxy groups
A phenyl group which may have
Pyrenyl, naphthyl, phenanthyl, or ethyl
Represents a rucarbazolyl group. )

Embedded image (In the formula, n is 0 or 1, m is 1 or 2, R ¹ and R ² are a hydrogen atom, a methyl group, and Ar is a halogen atom, a cyano group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group as a substituent. Or —NR ⁵ R ⁶ group (where R ⁵ and R ^{6 each} have 1 carbon atom)
To 4 alkyl groups, an aralkyl group having 1 to 4 carbon atoms,
Is an alkyl group having 1 to 4 carbon atoms as a substituent,
Substituted or unsubstituted aryl having 1 to 4 alkoxy groups
A phenyl group which may have
Pyrenyl group, a naphthyl group, Fenanchi group or ethyl,
Represents a rucarbazolyl group. )

Further, according to the present invention, the following general formula (2)
The novel phosphonate derivative represented by these is provided.

Embedded image (In the formula, R ³ represents an alkyl group having 1 to 4 carbon atoms .)
In the general formula (1), Ar represents a monovalent or divalent group of an aromatic hydrocarbon group, and specific examples of the monovalent group include non-condensed carbon rings such as a phenyl group, a biphenylyl group, and a terphenyl group. In addition to the aromatic groups of the formula, mention may be made of fused polycyclic hydrocarbon groups. In this case, as the condensed polycyclic hydrocarbon group, those having 18 or less carbon atoms forming a ring are preferable, such as a pentalenyl group, an indenyl group, a naphthyl group, an azulenyl group, a heptalenyl group, a biphenylenyl group, and an as-indacenyl. Group, fluorenyl group, S-indacenyl group, acenaphthylenyl group, preyadenyl group,
Examples include an acenaphthenyl group, a phenalenyl group, a phenanthryl group, an anthryl group, a fluoranthenyl group, an acephenanthrenyl group, an aceanthrenyl group, a triphenylenyl group, a pyrenyl group, a chrysenyl group, and a naphthacenyl group. Further, the aromatic hydrocarbon group can have the following substituents. (1) Halogen atom, cyano group, nitro group (2) Alkyl group, preferably C ₁ -C _12, especially C ₁ -C ₈ , more preferably C ₁ -C ₄ linear or branched alkyl group And these alkyl groups are further substituted with a fluorine atom, a hydroxyl group, a cyano group, a C ₁ -C ₄ alkoxy group, a phenyl group or a halogen atom, a C ₁ -C ₄ alkyl group or a C ₁ -C ₄ alkoxy group. May contain a substituted phenyl group. Specifically, a methyl group, an ethyl group, n-
Propyl, i-propyl, t-butyl, s-butyl, n-butyl, i-butyl, trifluoromethyl, 2-hydroxyethyl, 2-cyanoethyl,
2-ethoxyethyl group, 2-methoxyethyl group, benzyl group, 4-chlorobenzyl group, 4-methylbenzyl group,
4-methoxybenzyl group, 4-phenylbenzyl group and the like. (3) alkoxy group (—OR ⁴ ); R ⁴ represents an alkyl group defined in (2). Specifically, methoxy, ethoxy, n-propoxy, i-propoxy, t-
Butoxy, n-butoxy, s-butoxy, i-butoxy, 2-hydroxyethoxy, 2-cyanoethoxy, benzyloxy, 4-methylbenzyloxy, trifluoromethoxy and the like. (4) Aryloxy group: Examples of the aryl group include a phenyl group and a naphthyl group. It may contain a C ₁ -C ₄ alkoxy group, a C ₁ -C ₄ alkyl group or a halogen atom as a substituent. Specifically, a phenoxy group, a 1-naphthyloxy group, a 2-naphthyloxy group,
-Methylphenoxy group, 4-methoxyphenoxy group, 4
-Chlorophenoxy group, 6-methyl-2-naphthyloxy group and the like. (5) Alkyl mercapto group (-SR ⁴ ); R ⁴ represents the alkyl group defined in (2). Specific examples include a methylthio group, an ethylthio group, a phenylthio group, and a p-methylphenylthio group. (6)

Embedded image (Wherein R ⁵ and R ⁶ each independently represent a hydrogen atom, an alkyl group or an aryl group as defined in (2), and examples of the aryl group include a phenyl group, a biphenyl group, and a naphthyl group. Is a C ₁ -C ₄ alkoxy group,
It may contain a C ₁ -C ₄ alkyl group or a halogen atom as a substituent. R ₂ and R ₃ may form a ring together. Further, a ring may be formed together with a carbon atom on the aryl group. Specifically, amino, diethylamino, N-methyl-N-phenylamino, N, N-diphenylamino, N, N-di (p-tolyl) amino, dibenzylamino, piperidino , A morpholino group, a urolidyl group and the like. (7) An alkylenedioxy group or an alkylenedithio group such as a methylenedioxy group or a methylenedithio group. In the above general formula 1, the alkyl groups of R ¹ and R ² are C _{1 to} C ₁₂ , especially C ₁ to C ₁₂ .
C ₈ , and more preferably C ₁ -C ₄ linear or branched ones, and specific examples include methyl, ethyl, n-propyl, i-propyl, t-butyl, and s- Butyl group, n-butyl group, i-butyl group, trifluoromethyl group, 2-hydroxyethyl group, 2-cyanoethyl group,
-Ethoxyethyl group, 2-methoxyethyl group, benzyl group, 4-chlorobenzyl group, 4-methylbenzyl group,
-Methoxybenzyl group, 4-phenylbenzyl group and the like. In addition, these alkyl groups are a fluorine atom,
Hydroxyl group, cyano group, C ₁ -C ₄ alkoxy group, phenyl group or halogen atom, C ₁ -C ₄ alkyl group or C
The ₁ -C ₄ substituents of the phenyl group substituted with an alkoxy group may contain.

The olefin compound represented by the general formula 1 according to the present invention is a novel substance, and the compound is a phosphonic acid ester derivative represented by the general formula 2;
That is, it is obtained by reacting 1-pyrenylmethylphosphonic acid ester with a carbonyl compound represented by the above general formula 3 in the presence of a basic compound.
In this case, as the basic compound, that is, the basic catalyst,
Mention may be made of caustic soda, caustic potash, sodium amide, sodium and sodium hydride, alcoholates such as potassium tert-butoxide. Further, as a reaction solvent, methanol, ethanol, isopropanol, butanol, 2-methoxyethanol,
1,2-dimethoxyethane, bis (2-methoxyethyl) ether, dioxane, tetrahydrofuran, toluene, xylene, dimethylsulfoxide, N, N-dimethylformamide, N-methylpyrrolidone, 1,3-dimethyl-2-imidazolidinone And the like. Among them, polar solvents such as N, N-dimethylformamide and dimethylsulfoxide are preferred.

[0010] The reaction temperature is 1) the stability of the solvent used to the basic catalyst, 2) the condensation component [general formula 2 and 3
3) can be selected widely depending on the reactivity of the basic catalyst as a condensing agent in a solvent. For example, when a polar solvent is used, the temperature is actually from room temperature to 100 ° C, preferably from room temperature to 80 ° C. However, higher temperatures may be used if the reaction time is reduced or a less active condensing agent is used.

The 1-pyrenylmethylphosphonate represented by the general formula 2 used in the present invention is:
It is a new substance not described in the literature. R in the general formula 2
The lower alkyl group of ³ is preferably an alkyl group having 1 to 4 carbon atoms, particularly a methyl group and an ethyl group. The phosphonate derivative can be easily produced by heating the corresponding halomethyl compound and the trialkyl phosphite directly or in a solvent such as toluene or xylene.
Here, as the trialkyl group of phosphorus trialkyl,
An alkyl group having 1 to 4 carbon atoms, particularly a methyl group and an ethyl group are preferred. The usage ratio of the trialkyl phosphite to the halomethyl compound is 1 to 10 equivalents, preferably 2 to 4 equivalents. The reaction is usually carried out at a temperature of about 80 to 160 ° C, preferably around 100 to 140 ° C.

Further, Ar and R ¹ in the general formula (3)
And R ² are Ar, R ¹ and R ² in the above general formula 1.
And when m = 2, a typical example of the compound represented by the general formula 3 is phthalaldehyde,
Isophthalaldehyde, terephthalaldehyde, naphthalenedicarbaldehyde, 2,4-hexadiene-1,6
-Dial, 2,5-dimethoxy terephthalaldehyde and the like.

[0013]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail with reference to embodiments.

Reference Example 1 [Production of 1- (4-methylstyryl) pyrene] 2.47 g of diethyl 1-pyrenylmethylphosphonate (7
mmol) and 0.84 g of 4-methylbenzaldehyde
(7 mmol) in N, N-dimethylformamide (D
MF) dissolved in 25 ml with stirring, and 1.62 g of sodium methylate (a methanol solution containing 28% by weight) (7 ×
1.2 mmol) is added slowly so that the temperature of the system does not exceed 30 ° C. Thereafter, the mixture is stirred at room temperature for 1 hour, neutralized with acetic acid, diluted with about 300 ml of water, and then the crystals are collected by filtration. After drying the obtained crystals, column purification was performed twice (first time: carrier; silica gel, eluent; toluene / n-hexane = 1/1, second time: carrier; silica gel, eluent; toluene / n-hexane = 1/2) yellow powder 2.2
1 g (93.5% yield) was obtained. Furthermore, the obtained yellow powder was recrystallized with a mixed solvent of toluene / n-hexane to obtain 1- (4-methylstyryl) pyrene as yellow needle crystals. The melting point of the obtained compound is 152.7-153.
5 ° C.

Embodiment1~9 reference Used in Example 14-methylbenzaldehyde
Instead of Table 1 to Table2Using the carbonyl compound shown in
Except for the above, the same procedure as in Example 1 was repeated to convert the olefin compound.
Obtained. Table 1-Table2Shown in

The infrared absorption spectra (KBr tablet method) of each compound obtained in Examples 4 and 5 are shown in FIGS.

[Table 1]

[Table 2]

Embodiment6  [1-methyl-1- (p-chlorophenyl) -2- (1
Production of -pyrenyl) ethylene] 2.47 g of diethyl 1-pyrenylmethylphosphonate (7
mmol) and 1.08 g of p-chloroacetophenone
(7 mmol) was dissolved in 25 ml of DMF with stirring.
1.24 g of mu-tert-butoxide (7 × 1.5 mm
ol) is added slowly over 2 hours. Then to room temperature
And heat stirring at 60 ° C. for 9 hours. Acetic acid
After further neutralization, extraction with toluene, washing with water, and then sulfuric acid
Dry over magnesium and concentrate under reduced pressure. The obtained knot
After drying the crystals, column purification (carrier; silica gel, eluent;
Toluene / n-hexane = 1/1), yellow powder
1.12 g (44.8%) were obtained. Furthermore, toluene / n
Recrystallization with a mixed solvent of -hexane gave yellow crystals.
Was. This is washed by heating with 100 ml of ethanol,
Crystal of 1-methyl-1- (p-chlorophenyl) -2-
A pure product of (1-pyrenyl) ethylene was obtained. Compound obtained
The melting point of the product is 161.6-163.7 ° C,
The analysis values were as follows.FIG. 3 shows the infrared absorption spectrum (KBr tablet method).

Embodiment7,8  [Β, β'-bis (1-pyrenyl) -1,4-divinyl
Production of benzene] 1-pyrenylmethylphosphonic acid diethyl
3.52 g (10 mmol)The carbonyl shown in Table 3
Compound(5 mmol) was dissolved in 30 ml of DMF.
1.68 g of potassium tert-butoxide (15
mmol) at 22-29 ° C. Room temperature after addition
After stirring for an hour, dilute with 30 ml of methanol and crystallize.
It was collected by filtration. After washing with water and then with methanol, heat under reduced pressure
Drying gave the product. N, N-dimethylacetamide
Recrystallized fromOlefin compounds shown in Table 3I got

[Table 3]

Embodiment9  [Production of diethyl 1-pyrenylmethylphosphonate] 120 g (0.48 mol) of 1-chloromethylpyrene was added to
Dissolve in 500 cc of triethyl phosphate, 125-140
Stir at 5 ° C. for 5 hours. Ethyl chloride generated during the reaction
Rides are excluded from the system. After cooling, 370 cc of n-hexane
Was added dropwise to precipitate crystals, which were collected by filtration.
After washing twice with 300cc, heat and dry under reduced pressure
151.4 g of crude diethyl enylmethylphosphonate
(89.7% yield). Furthermore, n-hexane, vinegar
Recrystallization was performed with a mixed solvent of ethyl acetate to obtain white needle-like crystals.
-A pure product of diethyl pyrenylmethylphosphonate was obtained. Fusion
Point: 115.0-116.0 ° C. Infrared absorption spectrum of this compound
Vector4Shown in The elemental analysis values are as follows.
It was.The following bisazo compound 5 as a charge generating substance
 7.5 copies

[0020]

The novel olefin compound containing a pyrene ring represented by the above general formula (1) according to claim (1) has a molecular structure in which π conjugation is expanded by the pyrene ring, and thus is an organic electronized material. It is particularly useful as Further, according to the production method of claim (2), the olefin compound having a high yield and a high purity is obtained by a condensation reaction of a phosphonate derivative with various carbonyl compounds in a short time under extremely mild conditions. be able to. Further, the phosphonic acid derivative of claim (3) is extremely useful as an intermediate of the olefin compound represented by the general formula 1 containing a pyrene ring.

[Brief description of the drawings]

FIG. 1 is an infrared absorption spectrum diagram (kBr tablet method) of the olefin compound obtained in Example 2 .

FIG. 2 is an infrared absorption spectrum diagram (kBr tablet method) of the olefin compound obtained in Example 3 .

FIG. 3 Infrared ray of the olefin compound obtained in Example 6
It is an absorption spectrum figure (kBr tablet method).

FIG. 4 is an infrared absorption spectrum diagram (kBr tablet method) of the phosphonic acid derivative obtained in Example 9 .

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification code FI C07C 211/48 C07C 211/48 C07D 209/86 C07D 209/86 C07F 9/40 C07F 9/40 Z G03G 5/06 314 G03G 5 / 06 314Z (72) Inventor Hiroshi Adachi 1-3-6 Nakamagome, Ota-ku, Tokyo Inside Ricoh Co., Ltd. (56) References JP-A-3-138804 (JP, A) JP-A-3-93736 ( JP, A) JP-A-2-210357 (JP, A) JP-A-1-252965 (JP, A) JP-A-58-42053 (JP, A) JP-A-55-67751 (JP, A) JP-A-55-69652 (JP, A) JP-A-50-135061 (JP, A) JP-A-50-138837 (JP, A) Phys. Chem. Vol. 13 (1984) p. 2714-p. 2718 Bull. Soc. Chim. Fr. , No. 3 (1967) p. 955-p. 960 Chem. Ber. , Vol. 93, (1960) p. 1799-p. 1809 (58) Field surveyed (Int. Cl. ⁷ , DB name) CA (STN) CAOLD (STN) REGISTRY (STN)

Claims (3)

(57) [Claims] 1. A novel olefin compound represented by the following general formula (1) . Embedded image Wherein n is 0 or 1, m is 1, Ar, R ¹ ,
R ² , n and m each represent the following. n =
When 0 and m = 1, R ¹ represents a hydrogen atom, Ar represents a methoxynaphthyl group, and when n = 1 and m = 1, R ¹ represents a hydrogen atom, R ² represents a hydrogen atom or a methyl group, Ar Is a dimethylamino-substituted phenyl group, or methoxy
Represents a substituted phenyl group. ) Wherein a carbonyl compound represented by the following general formula phosphonate derivative with the following general formula represented by (2) (3), the following general formula which comprises reacting in the presence of a basic compound A method for producing the olefin compound represented by (1) . Embedded image (In the formula, R ³ represents an alkyl group having 1 to 4 carbon atoms .) (Where n is 0 or 1, m is 1 or 2, R ¹ and R ² are
A hydrogen atom, a methyl group or Ar is a halogen atom as a substituent.
, Cyano group, alkyl group having 1 to 4 carbon atoms, alkoxy
Or —NR ⁵ R ⁶ group (where R ⁵ and R ^{6 each} have 1 carbon atom)
To 4 alkyl groups, an aralkyl group having 1 to 4 carbon atoms,
Is an alkyl group having 1 to 4 carbon atoms as a substituent,
Substituted or unsubstituted aryl having 1 to 4 alkoxy groups
A phenyl group which may have
Pyrenyl, naphthyl, phenanthyl, or ethyl
Represents a rucarbazolyl group. ) (Where n is 0 or 1, m is 1 or 2, R ¹ and R ² are
A hydrogen atom, a methyl group or Ar is a halogen atom as a substituent.
, Cyano group, alkyl group having 1 to 4 carbon atoms, alkoxy
Or —NR ⁵ R ⁶ group (where R ⁵ and R ^{6 each} have 1 carbon atom)
To 4 alkyl groups, an aralkyl group having 1 to 4 carbon atoms,
Is an alkyl group having 1 to 4 carbon atoms as a substituent,
Substituted or unsubstituted aryl having 1 to 4 alkoxy groups
A phenyl group which may have
Pyrenyl, naphthyl, phenanthyl, or ethyl
Represents a rucarbazolyl group. ) 3. A phosphonic acid ester derivative represented by the following general formula (2). Embedded image (In the formula, R ³ represents an alkyl group having 1 to 4 carbon atoms .)