KR100449854B1 - Spirobifluorene compound with alkyl substituents and the preparation thereof - Google Patents

Abstract

The present invention relates to a novel spirobifluorene-based compound and a method for producing the same, and more particularly, to a spirobifluorene-based compound having a structure of the following formula (1) and a method for producing the same.

(In Formula 1, R ₁ , R ₂ are the same or different C ₁ -C ₂₀ linear or branched alkyl group, alkoxy group or thioalkyl group, X ₁ , X ₂ is a halogen element.) The compound may be used as an organic dye laser material, a blue organic electroluminescent device material, a nonlinear optical material, and an electronic material material having a molecular size.

Description

Spirobifluorene compound with alkyl group and its preparation method

The present invention relates to a novel spirobifluorene compound, a method for preparing the same, and in particular, in one fluorene ring, one fluorene ring is optionally substituted with an alkyl group at a desired position to increase solubility in a general solvent. The other fluorene ring is provided with a compound into which a halogen group is introduced to introduce a functional group or a polymer having a two-dimensional structure, and a method for producing the same.

Until now, various kinds of spirofluorene-based compounds used for organic dye laser materials, blue organic light emitting device materials, nonlinear optical materials, and electronic material materials having molecular sizes have been synthesized.

Looking at specific examples related to the known spirobifluorene compounds, Kreuder et al. (Kreuder, Willi; Yu, Nu; Salbeck, Josef) disclose a spirofluorene laser dye material having a conjugation system in patent WO 9940665. It is disclosed that it can be used as.

Spritzer et al. (Spreitzer, Hubert; Salbeck, Josef; Weissoertel, Frank) are representative materials that can be used as laser dyes in German patent DE 19804310, with 4 bromine groups substituted at the 2,2 ', 7,7'-positions. Spirobifluorene monomers 2,2 ', 7,7'-tetrabromo-9,9'-spirobi [9H-fluorene] and derivatives 2,2', 7,7'-tetrakis (9, A process for preparing 9'-spirobi [9H-bifluorene] -2-yl) -9,9'-spirobibi [9H-bifluorene] is disclosed.

Lupo et al. (Lupo, Donald; Salbeck, Josef; Schenk, Hermann; Stehlin, Thomas; Stern, Roland; Wolf, Arno; Kreuder, Willi) in US Pat. No. 5,840,217 in 2,7- or 2,2'-position 2 Methods for synthesizing 2,7-dibromo-9,9'-spirobifluorene and 2,2'-dibromo-9,9'-spirobifluorene substituted with the same bromine group and derivatives thereof It is disclosed that it can be used as an organic electroluminescent material.

In Salbeck, Josef; Kreuder, Willi, patent WO 9818996, a representative material is 2,2 ', 4,4', 7,7'-hexakis (4-biphenylyl) -9,9'-spir It discloses a method for preparing rubifluorene and that it can be used as a photobleach.

Lupo, Donald; Salbeck, Josef discloses in European patent EP 768563 that spirobifluorene with a conjugation system can be used as a nonlinear optical material.

In addition, Convergent Synthetic Routes to Orthogonally Fused Conjugated Oligomers Directed Toward Molecular Scale Electronic Device Applications, J. Org.Chem, Wu, Ruilian; Schumm, Jeffry S .; Pearson, Darren L .; Tour, James M (1996), 61 (20), 6906-6921) and by Thor, James M .; Wu, Ruilian; Schumm, Jeffrey S, Synthesis of orthogonally fused conducting oligomers for molecular electronic devices, Polym. Prepr 1992, 33 (1), 1092-3 disclose that spirobifluorene with polythiophene can be applied to electronic materials and devices having a molecular size.

As such, the spirobifluorene compound has its own monomer in which 4 bromine elements are substituted at the 2,2 ', 7,7'- position or 6 bromine elements at the 2,2', 4,4 ', 7,7'- position. B or derivatives thereof have been prepared and used for organic dye laser material, blue organic electroluminescent device material, nonlinear optical material, and electronic material material having molecular size.

However, the above-mentioned spirobifluorene compounds have all four or six substituent positions having the same degree of activity, thereby limiting the preparation of derivatives having different functionalities at the desired positions. In particular, since it is active in all four or six positions, it was not possible to make a polymer having a two-dimensional structure using the monomer.

In addition, 2,7-dibromo-9,9'-spirobifluorene and 2,2'-dibromo-9 having two identical bromine groups substituted in the 2,7- or 2,2'- positions, Since 9'-spirobifluorene is known, polymer synthesis has been attempted from these monomers, but it has been limited in practical use because it is almost insoluble in a general solvent, and development of a new compound that can solve this problem is difficult. Has been requested.

In order to solve the problems of the prior art as described above, an object of the present invention is to provide a spirobifluorene compound each having a different substituent on the two fluorene ring.

1 is a Nuclear Magnetic Resonance (NMR) spectrum of protons of Compound V-1.

2 is a nuclear magnetic resonance spectrum of carbon of compound V-1.

3 is a nuclear magnetic resonance spectrum of a proton of compound V-2.

4 is a nuclear magnetic resonance spectrum of carbon of compound V-2.

In order to achieve the above technical problem, the present inventors have conducted research, and substituted one alkyl group with one of two fluorene rings of a spirobifluorene compound to increase solubility in a solvent. On the other hand, the present invention has been completed by successfully preparing a compound in which two halogen groups are introduced for introducing functional groups.

The present invention provides a spirobifluorene compound having a structure of formula (1).

(Formula 1)

(In Formula 1, R ₁ , R ₂ are the same or different C ₁ -C ₂₀ linear or branched alkyl group or alkoxy group or thioalkyl group, X ₁ and X ₂ are the same or different hydrogen or halogen element or A hydroxyl group or boric acid or boric ester, provided that X ₁ and X ₂ do not simultaneously represent hydrogen.)

R ₁ and R ₂ in the substituents of the spirobifluorene compound having the structure of Formula 1 are symmetrically positioned in each ring, or 8 'and 2', 8 'and 3', 8 'and 4', 7 'And 1', 7 'and 3', 7 'and 4', 6 'and 1', 6 'and 2', 6 'and 4', 5 'and 1', 5 'and 2' or 5 ' It is preferably located at 3 'carbon.

The present invention also provides a method for preparing a dialkyl (or dialkoxy, or dithioalkyl) biphenyl compound by substituting an alkyl group or an alkoxy group or a thioalkyl group to a biphenyl compound, and the dialkyl (or dialkoxy, or It provides a method of producing a compound having the structure of Formula 1 comprising the step of reacting a dithioalkyl) biphenyl-based compound with a halogenated fluorenone.

The present invention also provides an organic light emitting device comprising the compound having the structure of Formula 1, wherein the organic light emitting device has an organic functional layer including at least one light emitting layer between a pair of electrodes, the organic It is preferable that a functional layer contains the compound which has a structure of the said General formula (1).

In the present invention, a schematic diagram of a synthetic route for synthesizing spirobifluorene substituted with an alkoxy group is shown in Scheme 1 below.

In the above scheme, R is an alkyl group, R ₁ , R ₂ are the same or different C ₁ -C ₂₀ linear or branched alkyl group, X, X ₁ and X ₂ is a halogen element.

The reaction scheme is to introduce a unit having an alkyl group at a desired position of the 3 ', 6'- and 1', 6'- position of the spirobifluorene compound and having activity only at two positions, not 4 and 6 positions. It is a reaction scheme showing a route for synthesis.

First, to make a spiro compound, a halogen element must be fixed at the 2-position of biphenyl. Several different types of 2-bromobiphenyl derivatives substituted with one or two alkoxy substituents are described by Sparling, J .; Fung, D .; Safe, S. (Biomed. Mass Spectrom. (1980). ), 7 (1), 13-19).

In the above scheme, 2-halogenated dialkoxybiphenyl is used as a starting material for synthesizing Compound V-1 according to the present invention and V-2 having a geometric isomer relationship. First, compound I can be prepared by mono-halogenation of dialkoxybiphenyl, the preparation method of which is Jardrue et al. (Jandrue, Charles E .; Kampe, Marcis M .; Simon, Myron S .; Waller, David P .; Whritenour, David C), WO 9304403 and Geiger, Suzanne; Joannic, Michel; Pesson, Marcel; Techer, Henri; Legrange, E .; Aurousseau, Michel (Chim. Ther. (1966), (7), 425-37.

Compound II is then obtained by substituting two alkoxy groups with two hydroxy group groups in order to adjust the alkyl chain length. Similar reactions are disclosed in Tetrahedron, 1968, 24, 2289 by JFW McOmie; ML Watts; DE West. Thereafter, compound II having two hydroxyl groups and alkylhalogen having different chain lengths are reacted to obtain compound III of C ₂ , C ₆ , C ₈ , C ₁₂ and C ₂₀ .

Compound IV is obtained by adding 2,7-dihalogenated fluorene-9-one to the obtained compound III. At this time, a metal-ligand substitution reaction may be used, and the present inventors have carried out a metal-ligand substitution reaction with a halogen ligand of lithium metal and compound III at a temperature of about −78 ° C., followed by 2,7-dihalogenated fluorene- Compound IV was prepared using a method of adding 9-one, in which a slightly excess amount of 2,7-dihalogenated flu was used to prevent the exchange reaction of halogen ligands and metals of 2,7-dibromofluorenone. It is preferable to add orenone.

Subsequently, compounds V-1 and V-2 having a geometric isomer relationship are obtained by the cyclization reaction of Compound IV. As a last step, the cyclization reaction may be performed by stirring with polyphosphoric acid at a temperature of about 50-60 ° C. This cyclization reaction occurs because electrons can be easily given at the 2,4-position of the alkoxy group. It can be seen that. In particular, V-1 produced at the 4-position, which can give electrons more easily than the 2-position, can be obtained at higher yield when the reaction temperature is lowered.

A schematic route for synthesizing spirobifluorene substituted with alkyl or thio alkyl groups in the compound according to the present invention is shown in Scheme 2 below.

Wherein R ₁ and R ₂ are the same or different C ₁ -C ₂₀ linear or branched alkyl groups or thioalkyl groups, and X, X ₁ and X ₂ are halogen elements.

In order to synthesize spirobifluorene substituted with alkyl or thio alkyl groups, 3,3'-dihalogenated biphenyl is first reacted with alkylthiol to obtain Compound VI, and then Compound VII is obtained through a single halogenation reaction. Compound IX can be obtained by the same method as in Scheme 1.

Hereinafter, the present invention will be described in more detail with reference to Examples.

(Example)

(1) Preparation of 2-bromo-5,3'-dimethoxybiphenyl (Compound I)

First, 3,3'-dimethoxybiphenyl (5.0 g, 23.34 mmol) was dissolved in 52 ml of dimethylformamide solvent and cooled to 0 ° C. N-bromosuccinimide (4.15 g, 23.34 mmol) was dissolved in 63 ml of dimethylformamide solvent and the solution was added very slowly to the 3,3'-dimethoxybiphenyl solution for about 1.5 hours. The resulting mixture was stirred at room temperature for about 12 hours, and after distilled water was added and stirred for about 10 minutes, extracted three times with nucleic acid, the extract solution was washed three times with distilled water, dried over sodium sulfate, and hexane was removed under reduced pressure. 6.70 g) was obtained. Yield 98%. Nuclear magnetic resonance (NMR) spectra showed that the product had a structure consistent with 2-bromo-5,3'-dimethoxybiphenyl (Compound I).

(2) Preparation of 6-bromo-biphenyl-3,3'-diol (Compound II)

Boron tribromide (1M concentration, 137 ml, 137.12 mmol) dissolved in dichloromethane was slowly added to the compound I (6.70 g, 22.85 mmol) obtained in (1) while maintaining the solution at 0 ° C. for 1 hour. . The stirred solution was raised to room temperature and stirring continued for about 12 hours. A small amount of ice water was slowly added to the reaction mixture, followed by extraction three times with dichloromethane. The extract solution was washed three times with distilled water, dried over sodium sulfate, and the dichloromethane solvent was removed under reduced pressure to obtain a residue. Chromatographic purification on silica gel using 4% ethyl acetate in dichloromethane gave 6-bromo-biphenyl-3,3'-diol (5.92 g, Compound II) in a yield of 98%. Nuclear magnetic resonance spectra confirmed that the product had a structure consistent with Compound 2.

(3) Preparation of 2-bromo-5,3'-bis-octyloxy-biphenyl (Compound III)

6-bromo-biphenyl-3,3'-diol (5.92 g, 22.43 mmol) obtained in the above (2), octane 1-bromide, potassium carbonate (18.60 g, 134.56 mmol), and potassium iodide (3.72 g, 22.43 mmol) was dissolved in dimethylformamide (60 mL) and then heated for 24 hours while maintaining a temperature of about 150 ° C. After cooling to room temperature, distilled water was added and stirred for about 10 minutes, followed by extraction three times with hexane. The extract solution was washed three times with distilled water, dried over sodium sulfate, and the hexane was concentrated under reduced pressure. Chromatographic purification on silica gel using 4% dichloromethane in hexanes gave 2-bromo-5,3'-bis-octyloxy-biphenyl (6.36 g, compound III) in a yield of 58.1%. Nuclear magnetic resonance spectra and elemental analysis data confirmed that the product had a structure consistent with compound III.

(4) Preparation of 9- (5,3'-bis-octyloxy-biphenyl-2-yl) -2,7-dibromo-9H-fluorene-9-ol (compound IV)

2-bromo-5,3'-bis-octyloxy-biphenyl (0.598 g, 1.225 mmol) obtained in (3) was dissolved in dried tetrahydrofuran (30 mL), and then cooled to -78 ° C. Tertiary butyllithium (1.7 M, 1.44 mL, 2.45 mmol) was added very slowly. The resulting product was stirred for 1 hour while maintaining the temperature of -78 ° C. After 1 hour, 2,7-dibromofluorene-9-one (0.497 g, 1.47 mmol) dissolved in dried tetrahydrofuran (20 mL) was added very slowly, stirred for 1 hour, and then cooled to room temperature. Stirring for more than half an hour at room temperature while raising. After completion of the reaction by adding a small amount of distilled water, saturated brine was added, the organic layer was extracted twice with ether, dried over sodium sulfate, and the ether was concentrated under reduced pressure. Chromatographic purification on silica gel using a 30-40% dichloromethane system of hexanes to provide 9- (5,3'-bis-octyloxy-biphenyl-2-yl) -2,7-dibromo-9H-flu Oren-9-ol (0.62 g, Compound IV) was obtained in 68% yield. Nuclear magnetic resonance spectra and elemental analysis showed that the product had the structure of Compound IV.

(5) 2,7-dibromo-3 ', 6'-bisoctyloxy-9,9'-spirobifluorene (Compound V-1) and 2,7-dibromo-1', 6 ' Preparation of -bisoctyloxy-9,9'-spirobifluorene (Compound V-2)

Polyphosphoric acid (6 mL) was mixed with Compound IV (0.5 g, 0.668 mmol) and stirred for 24 hours while maintaining 60 ° C. After cooling to room temperature, a small amount of distilled water was added to terminate the reaction. The organic layer was extracted twice with dichloromethane, dried over sodium sulfate, and the dichloromethane was concentrated under reduced pressure. Chromatographic purification on silica gel using 4% dichloromethane in hexanes gave 2,7-dibromo-3 ', 6'-bisoctyloxy-9,9'-spirobifluorene (0.24 g, compound V- 1) in 49% yield and also its geometric isomer 2,7-dibromo-1 ', 6'-bisoctyloxy-9,9'-spirobifluorene (0.24 g, compound V-2) Were each obtained with a yield of 49%.

V-2 preferentially eluted, and the relative amount of V-1 increased by about 70% at 40 ° C than at a reaction temperature of 60-100 ° C.

Nuclear magnetic resonance spectra confirmed that each product had a structure consistent with compounds V-1 and V-2. 1 and 2 show the proton nuclear magnetic resonance spectra and carbon nuclear magnetic resonance spectra of compound V-1, respectively, and FIGS. 3 and 4 show the proton nuclear magnetic resonance spectra and carbon nuclei of compound V-2, respectively. Show the magnetic resonance spectrum.

Although it is not possible to enumerate all of the methods for preparing a large number of compounds according to the present invention, the following examples are described only through the same reaction route as in Scheme 1 in which alkoxy is substituted. It is obvious to those skilled in the art that various modifications are possible therefrom. Therefore, the true technical protection scope of the present invention will be defined by the technical spirit of the appended claims.

As described above, according to the present invention, a variety of spirobifluorene compounds may be prepared by selectively introducing a desired substituent at a desired position. Thus, it is possible not only to prepare derivatives having different functionalities but also excellent solubility. It can be usefully used for the synthesis of the polymer used, and can be used as an electronic dye material having an organic dye laser material, a blue organic light emitting device material, a nonlinear optical material and a molecular size.

Claims (5)

A spirobifluorene compound having a structure of Formula 1 below. (Formula 1) (In Formula 1, R ₁ , R ₂ are the same or different C ₁ -C ₂₀ linear or branched alkyl group or alkoxy group or thioalkyl group, X ₁ and X ₂ are the same or different hydrogen or halogen element Provided that X ₁ and X ₂ do not represent hydrogen at the same time.) The method of claim 1, R ₁ and R ₂ are symmetrically positioned in each ring, or 8 'and 2', 8 'and 3', 8 'and 4', 7 'and 1', 7 'and 3', 7 'and Spirobifluorene compounds located at carbon of 4 ', 6' and 1 ', 6' and 2 ', 6' and 4 ', 5' and 1 ', 5' and 2 'or 5' and 3 '. Preparing a dialkyl (or dialkoxy or dithioalkyl) biphenyl compound by substituting any substituent selected from an alkyl group, an alkoxy group, and a thioalkyl group with a biphenyl compound; Method for preparing a compound having the structure of Formula 1 comprising the step of reacting the dialkyl (or dialkoxy or dithioalkyl) biphenyl-based compound with halogenated fluorenone. An organic light emitting device comprising the compound having the structure of Formula 1. The method of claim 4, wherein The organic light emitting device has an organic functional layer including at least one light emitting layer between a pair of electrodes, the organic electroluminescent device comprising a compound having the structure of formula (1).