TW201439050A - Synthesis method of oligo-anthracene and oligo-anthracene thereof - Google Patents

Abstract

A synthesis method of oligo-anthracene which a linear oligo-anthracene is synthesized by substitution reaction at a specific position of an anthracene oligomer and a linear structure oligo-anthracene synthesized by the synthesis method are disclosed. The synthesis method of oligo-anthracene includes: wherein X is H, OR is alkoxy group at C1, C4 position; X is halide; X is halide, OR is alkoxy group at C2, C3 position; or X is H, W is halide at C2 position, OR is alkoxy group at C1, C4 position.

Description

Method for synthesizing oligomeric molecules and their oligomers

The present invention relates to a method for synthesizing a ruthenium oligomer molecule; in particular, a method for synthesizing a ruthenium oligomer molecule which can form a linear ruthenium oligomer by a substitution reaction at a specific position of a ruthenium monomer, and a method based on the method Linear structure of fluorene oligomers.

In order to meet the market demand, todayadays, many portable display elements have been used to replace traditional displays. Recently, flexible displays based on plastics have attracted attention. Among them, conductive conjugated molecules based on organic materials are the most concerned. The conductive conjugated molecule has high compatibility with the plastic substrate, and the molecular transfer property can also be adjusted to a better state by structural modification, thereby increasing the molecular transport rate of the conductive conjugated molecule. And transfer type.

At present, most of the organic materials used as conductive conjugated molecules are pentacene with high charge transfer rate and high current switching ratio; but it is also difficult to process and poor chemical stability of pentacycline, which leads to Pentacyclin has great limitations in its application.

For the first reason, anthracene, which is also one of the polyacene derivatives and also has high conductivity, was born. For example, Patent Cases No. 201247676 and Announcement No. I359801 of the Republic of China, respectively, utilize different synthesis methods to form oligomer-derived molecules with a quinone-centered structure, and use these oligo-oligomer derived molecules to apply In an organic electronic device, a better electron or hole transfer effect is provided. However, the conventionally discovered oligomeric derivative molecules often hinder the known synthesis method and cannot replace their specific positions by functional groups. The poly-derivative molecules cannot complete the specific structural modification, and after all, they are only limited to the nonlinear structure, so the conduction effect is practically limited.

Moreover, the common 1,4-dimethoxyanthracene and 9,10-dimethoxyanthracene in the market are also hindered. The substitution of the functional group is not easy, and the oligomerization of the ruthenium molecule is rarely formed into an oligomer material such as a dimer or a trimer, so that the conductivity of the ruthenium molecule is sufficient to replace the pentacycline, but it is still unable to rely on the specific position. Structural modification gives a more significant improvement.

In view of this, it is indeed necessary to develop a synthesis method of a ruthenium oligomer molecule which is different from the conventional method, whereby the synthesis method can cause the ruthenium molecule to be oligomerized into a dimer or a trimer oxime oligomer, and simultaneously solve Various problems as described above.

The main object of the present invention is to improve the above problems to provide a method for synthesizing a ruthenium oligomer molecule which is capable of performing a substitution reaction at a specific position of a ruthenium molecule to complete a specific structural modifier.

A second object of the present invention is to provide a ruthenium oligomer having a linear structure and having a preferred charge transfer rate.

In order to achieve the foregoing object, the method for synthesizing an oligomeric molecule of the present invention comprises the following reactions:

Wherein X is H, OR is alkoxy and is at the C1, C4 position; or X is a halogen functional group and is at C6, OR is an alkoxy group and is at the C1, C4 position; or X is a halogen functional group, and OR is an alkane Oxyl and located at the C2, C3 position; or X is H, W is a halogen functional group and is located at C2, OR is an alkoxy group and is located at the C1, C4 positions.

The method for synthesizing an oligomeric molecule according to the first aspect of the patent application, wherein the 2-bromo-1,4-dimethoxyanthracene of the formula (A3) is prepared,

The system consists of the following steps:

a) co-reacting with starting material A with potassium carbonate, acetone and dimethyl sulfate until compound A1 is produced;

b) the compound A1 is placed in an ice bath together with tetrahydrofuran and methanol, and sodium borohydride is added in portions to carry out a reaction to obtain an intermediate product A1', and the intermediate product A1' is continuously reacted with tetrafluorofuran to the same. Completely dissolved, adding stannous chloride until the reaction yields compound A2;

c) The reaction of the compound A2 with N-bromosuccinimide and dichloromethane until the compound A3 is produced, which is 2-bromo-1,4-dimethoxyfluorene.

Wherein, further comprising d) performing boronation reaction of the compound A3 to form a compound A4.

Here, the compound A3 and the compound A4 are coupled to a ruthenium dimer A5 which is 1,4-1', 4' TMDA.

Wherein, the 6-bromo-1,4-dimethoxyanthracene used to prepare the formula (B5) comprises the following steps:

The system consists of the following steps:

a) starting from B with potassium permanganate, pyridine and water, and after the reaction is completed and filtered and concentrated to remove pyridine, an aqueous solution is obtained, and the aqueous solution is extracted with acid water and ethyl acetate to obtain a compound. B1;

b) co-reacting with compound B1 with dichloromethane, acetic anhydride: until compound B2 is produced;

c) the compound B2 is added together with hydroquinone in a reaction mixture mixed with aluminum trichloride and sodium chloride, and the reaction is continued until the compound B3 is produced;

d) co-reacting with compound B3 with potassium carbonate, acetone, and adding dimethyl sulfate to continue to produce compound B4;

e) The compound B4 is placed in an ice bath together with tetrahydrofuran and methanol, and sodium borohydride is added in portions to carry out a reaction to obtain an intermediate product, and the intermediate product is dissolved in a tetrahydrofuran solution, and stannous chloride is added. Until the reaction yields the compound B5, the compound B5 is 6-bromo-1,4-dimethoxyanthracene.

Wherein, further comprising f) performing a boronation reaction with the compound B5 to form the compound B6.

Here, the compound B5 and the compound B6 were oligomerized to the oxime oligomer B7, and the oxime oligomer B7 was 5,8-5',8'TMDA.

Wherein, the 6-bromo-1,4-dimethoxyanthracene used to prepare the formula (C3) comprises the following steps:

The system consists of the following steps:

a) reacting compound B2 with phthalic acid and anhydrous dichloromethane, and adding aluminum chloride in portions, and continuing to act to produce a mixture of compound C1 and compound C1';

b) reacting a mixture containing the compound C1 and the compound C1' with concentrated sulfuric acid in an oil bath until the compound C2 is produced;

c) The compound C2 is placed in an ice bath together with tetrahydrofuran and methanol, and sodium borohydride is added in portions to carry out a reaction to obtain an intermediate product C2', and the intermediate product C2' is dissolved in a tetrahydrofuran solution and added. Stannous chloride until the reaction yields compound C3, which is 6-bromo-2,3-dimethoxyindole.

Further, d) is a boron esterification reaction of the compound C3 to produce a compound C4.

Here, the compound C3 and the compound C4 were oligomerized to a ruthenium oligomer C5 which was 6,7-6', 7'TMDA.

In order to achieve the foregoing object, the present invention further provides a method for synthesizing a ruthenium oligomer molecule, which comprises the following reactions:

Wherein X is substituted by a halogen functional group, and OR is an alkoxy group and is located at the C9 and C10 positions.

Wherein, the 2-bromo-9,10-dimethoxyanthracene used to prepare the formula (D2) comprises the following steps:

The system consists of the following steps:

a) Compound D1 is co-reacted with ethanol and sodium borohydride, and under the continuous action of potassium hydroxide and dimethyl sulfate, compound D2 is produced, and the compound D2 is 2-bromo-9,10-dimethoxy Basic.

Further comprising b) a boronation reaction with the compound D2 to give the compound D3.

Here, the compound D2 and the compound D3 were oligomerized to a fluorene oligomer D4, which was 9,10-9', 10'TMDA.

In order to achieve the aforementioned object, the oxime oligomer produced by the present invention by the aforementioned method is as follows:

Wherein, OR ₁ and OR ₂ may be located at C1, C4, C5, C8, C6, C7 or C9, C10 positions respectively; OR ₃ and OR ₄ may be located at C1, C4, C5, C8, C6, C7 or C9, C10, respectively. Position; and R ₁ , R ₂ , R ₃ , and R ₄ may be one of CH ₃ to C ₂₀ H ₄₁ and H ₂ C.

In order to achieve the foregoing object, the other oxime oligomer produced by the present invention by the aforementioned method is one of the following:

Wherein, OR ₁ and OR ₂ may be located at C1, C4, C5, C8, C6, C7 or C9, C10 positions respectively; OR ₃ and OR ₄ may be located at C1, C4, C5, C8, C6, C7 or C9, C10, respectively. And R ₁ , R ₂ , R ₃ , and R ₄ may be one of CH ₃ to C ₂₀ H ₄₁ and H ₂ C; and R ₅ and R ₆ may be CH ₃ to C ₂₀ H ₄₁ , H ₂ CC ≡C~C ₂₀ H ₂₁ -C≡C One of them.

Figures 1 to 4: Reaction structural formula of the oligomeric molecules of each configuration of the present invention.

Figure 5: Structural formula of the 蒽 dimer of each configuration of the present invention.

Figure 6: Structural formula of the trimer trimer of each configuration of the present invention.

The above and other objects, features and advantages of the present invention will become more apparent and obvious. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the following drawings: The method for synthesizing oligo-oligomers of the present invention can be used to synthesize various fluorene oligomers, which are widely used in organic materials. Flexible display; the following is a detailed description of the method for synthesizing an oligomeric molecule, and various oligomers produced by the method, and for the preferred embodiment of the present invention, for further details. The synthesis process of oligomeric molecules.

The general reaction of the oligomeric molecular synthesis method is as follows (detailed in Figure 1):

Wherein X is H, OR is alkoxy and is at the C1, C4 position; or X is a halogen functional group, OR is an alkoxy group and is at the C1, C4 position; or X is a halogen functional group, and OR is an alkoxy group and Located at the C2 and C3 positions; or X is H, W is a halogen functional group, OR is an alkoxy group and is located at the C1 and C4 positions.

Based on the forefront concept, the symmetrical aspect can also be disclosed in Equation 1. As will be understood by those skilled in the art, the corresponding reaction formula is not repeatedly shown here.

The general reaction of the method for synthesizing the oxime oligomer molecule of the present invention will be described in detail with reference to the following examples, and the reaction schemes described in Fig. 1 and the above will be referred to together. Among them, the present invention preferably selects bromine (Br) as the main halogen functional group, but is not limited thereto.

"A" 2-bromo-1,4-dimethoxyanthracene (2-bromo-1,4-dimethoxyanthracene, 2-bromo-1,4-DMA). The synthesis method consists of the following steps:

a) co-reacting with starting material A with potassium carbonate, acetone and dimethyl sulfate until compound A1 is produced; as detailed in reaction formula [A-1].

For example, in the present invention, the reaction between the respective compounds is selected by means of heating, reflux, extraction, precipitation, etc., so that a sufficient effect can be achieved between the respective compounds. In detail, in this embodiment, about 15 grams and 62.45 millimoles of the starting material A are selected to be placed in a double neck round bottom bottle, and an appropriate amount of potassium carbonate (preferably about 30.2 is added). And 21 ml of milliliters, and 350 ml of acetone, heated to reflux for about 1 hour; then add appropriate amount of dimethyl sulfate (dimethylsulfate; preferably about 23.63 grams and 187.3 millimoles), and continue After heating and refluxing for 48 hours and fully reacting, the acetone was removed by a rotary concentrator, and simultaneously extracted with dichloromethane and deionized water, and the organic layer was dried with anhydrous magnesium sulfate to remove water. The compound A1 was obtained as an orange solid by reprecipitation through dichloromethane and hexane; at this time, the yield of the compound A1 was about 95%. And the result of the analysis of the compound A1 is as follows: ¹ H-NMR (300 MHz, CDCL ₃ ) δ (ppm): 4.04 (s, 6H), 6.61 (s, 2H), 7.46-7.49 (m, 2H), 8.03 - 8.06 (m, 2H), 8.78 (s, 2H); ¹³ C-NMR (75 MHz, CDCl ₃ ) δ (ppm): 55.6, 100.9, 120.8, 125.5, 128.5, 131.5, 149.5.

b) The compound A1 is placed in an ice bath together with tetrahydrofuran and methanol, and sodium borohydride is added in portions to carry out a reaction to obtain an intermediate product A1', and the intermediate product A1' is continuously reacted with tetrahydrofuran until it is completely dissolved. Add stannous chloride until the reaction produces a compound A2; as detailed in the reaction formula [A-2].

For example, after the reaction of the compound [A-1] is carried out to obtain the compound A1, the present embodiment selects another 20 g of the compound A1 of 74.6 mmol to be placed in a one-side round bottom bottle, and is added. About 200 ml of tetrahydrofuran and about 200 ml of methanol, and place the flanking round bottom bottle in an ice bath, and then add an appropriate amount of sodium borohydride (preferably about 16.9 g and 446.7 millimolar), causing the compound A1 to continuously generate hydrogen gas during the reaction with the precursor substance, until the reaction is about 4 hours, then adding deionized water to stop the reaction; then, after removing the tetrahydrofuran and methanol aqueous solution by a rotary concentrator, adding dichloroethylene Dichloromethane and deionized water are extracted, and the organic layer is dried with anhydrous magnesium sulfate, and then precipitated through dichloromethane and hexane to obtain a beige solid intermediate A1'. Continue to introduce the intermediate product A1' into another flanking round bottom bottle, add about 350 mL of tetrahydrofuran, and add the appropriate amount of stannous chloride dihydrate (preferably about 31.3) after the intermediate product A1' is completely dissolved. And is 165.0 mmol), sustained at room temperature for about 5 to 6 hours. Also, after completion of the reaction, the compound A2 was obtained as a dark green solid by the same extraction and precipitation method as above; at this time, the yield of the compound A2 was about 95%. And the result of the analysis of the compound A2 is as follows: ¹ H-NMR (300 MHz, CDCl ₃ ) δ (ppm): 4.04 (s, 6H), 6.61 (s, 2H), 7.46-7.49 (m, 2H), 8.03-8.06 (m, 2H), 8.78 (s, 2H); ¹³ C-NMR (75 MHz, CDCl ₃ ) δ (ppm): 55.6, 100.9, 120.8, 125.5, 128.5, 131.5, 149.5.

c) reacting the compound A2 with N-bromosuccinimide and dichloromethane until the compound A3 is produced, which is 2-bromo-1,4-dimethoxyanthracene; Reaction formula [A-3].

For example, after the reaction of the compound [A-2] is carried out to obtain the compound A2, the present embodiment selects about 9.74 g and 40.8 mmol of the compound A2, and an appropriate amount of N-bromosuccinimide. (N-bromosuccinimide; preferably about 7.64 grams and 42.9 millimoles), and about 200 milliliters of dichloromethane are placed in another side-round round bottom bottle and reacted at room temperature for about 6-8 hours. And after extraction and precipitation, it is preferably purified by column chromatography (the extract is n-ethane) to obtain a yellow viscous liquid compound A3; at this time, the compound A3 The yield is about 85 to 90%. Further, the compound A3 was confirmed to be 2-bromo-1,4-dimethoxyanthracene, and the analysis results were as follows: ¹ H-NMR (300 MHz, CDCl ₃ ) δ (ppm): 4.05 (s) , 3H), 4.05 (s, 3H), 6.77 (s, 1H), 7.46-7.55 (m, 2H), 8.01-8.06 (m, 2H), 8.60 (s, 1H), 8.78 (s, 1H); ¹³ C-NMR (75 MHz, CDCl ₃ ) δ (ppm): 55.8, 61.3, 105.6, 110.6, 120.3, 122.0, 124.7, 125.8, 126.3, 127.0, 128.3, 128.6, 131.2, 132.2, 146.6, 152.2.

Accordingly, 2-bromo-1,4-dimethoxyfluorene having a halogen functional group at a specific position can be obtained via the preceding reaction step, and 2-bromo-1,4-dimethoxyanthracene can be obtained ( That is, the compound A3) is selected as an oligomeric monomer and then subjected to a boronation reaction to form an oligomeric precursor of the oligomerization reaction.

In detail, this embodiment can also be selected after the foregoing step c), and the other step d) is carried out by the boron esterification reaction of the compound A3 to form the compound A4; for example, the reaction formula [A-4].

For example, after the reaction formula [A-3] is obtained to obtain the compound A3 as an oligomeric monomer, the present embodiment is selected to be additionally added with potassium acetate (potassium acetate; preferably about 3.71 g and 37.84 m). A long-necked flank bottle of Mohr) is filled with about 3 grams of 9.46 millimoles of the compound A3, an appropriate amount of bis (pinacolato) diboron; preferably about 2.88 grams and 11.35. Milliole), an appropriate amount of [1,1'-bis(diphenylphosphino)ferrocene]palladium dichloride dichloride (1,1'-Bis(diphenylphosphino)ferrocene palladium(II) chloride complex With dichloromethane; preferably about 0.39 gram and 0.473 millimolar), and about 30 milliliters of anhydrous tetrahydrofuran, and heated under reflux for at least three days; until the reaction is completed and cooled, then the rotary concentrator The tetrahydrofuran was removed, and dichloromethane was added, and it was purified by column chromatography (extracted ethyl acetate / n-hexane = 1/10) to obtain a yellow and liquid compound A4; The yield of the compound A4 was about 60%, and the compound A4 was analyzed to confirm that it was 1,4-dimethoxy. Before becoming oligomers thereof, such as the following ^{results: 1 H-NMR (300 MHz} , CDCl 3) δ (ppm): 1.43 (s, 12H), 4.06 (s, 3H), 4.10 (s, 3H), 6.91 (s, 1H), 7.46-7.51 (m, 2H), 8.02-8.07 (m, 2H), 8.72 (s, 1H), 8.80 (s, 1H); ¹³ C-NMR (75 MHz, CDCl ₃ ) δ (ppm): 25.00, 55.65, 63.86, 83.67, 105.0, 121.2, 122.1, 125.6, 125.9, 127.3, 127.3, 128.6, 128.7, 131.7, 132.0, 150.9, 158.1.

Based on the above synthetic steps, in the present example, the compound A3 and the compound A4 can be obtained, and the compound A3 and the compound A4 are selected to be oligomerized to the oxime oligomer A5, which is 1,4-1. ',4'TMDA; as detailed in reaction formula [A-5].

For example, in this example, about 2.2 grams and 6.4 millimoles of the compound A4 are selected to be dissolved in methylene chloride, added to a flask, the dichloromethane is removed by a rotary concentrator, and the water is removed in a vacuum system. About 2.01 g of 6.72 mmol of this compound A3 was added with oxygen and nitrogen, and water and oxygen were again removed, followed by addition of about 30 ml of toluene, and degassing with nitrogen for about 30 minutes. After the degassing is completed, about 22 mL of an aqueous solution of sodium carbonate (the preferred molar concentration of the aqueous solution is 2 M) is slowly added, followed by the addition of Tetrakis (triphenylphosphine) palladium; preferably 0.35 g. 0.32 millimolar), and continue to heat to reflux, causing the solution to gradually change from yellow to black; continued, after extraction, precipitation, preferably can be purified by column chromatography (the extract is Methylene chloride / n-hexane = 1/10, ethyl acetate / n-hexane = 1/10) to give Compound A5 as a yellow solid; at this time, the yield of the compound A5 was about 58%. And the compound A5 was confirmed to be a 蒽 dimer molecule 1,4-1', 4'TMDA, and the analysis results were as follows: ¹ H-NMR (300 MHz, CDCl ₃ ) δ (ppm): 3.75 (s, 6H), 4.11 (s, 6H), 7.01 (s, 2H), 7.50-7.53 (m, 4H), 8.07-8.10 (m, 4H), 8.78 (s, 2H), 8.88 (s, 2H) ¹³ C-NMR (75 MHz, CDCl ₃ ) δ (ppm): 55.8, 61.3, 104.8, 121.2, 121.3, 125.0, 125.5, 125.6, 125.9, 127.7, 128.5, 128.7, 131.5, 132.0, 146.8, 151.3.

In this way, the method for synthesizing the oligo-oligomer of the present invention can obtain a fluorene-functional monomer having a halogen functional group by the preceding reaction step, and causes the bromine of the present embodiment to successfully replace the carbon number of the dimethyloxy hydrazine. In this way, the specific structural modification is completed, and the oligomeric molecule produced by the oligomerization of the monomer can have a linear structure; that is, the oligomer of the oligomer obtained by the oligomerization method of the oligomeric molecule of the present invention is removed. It maintains its own chemical stability and is more capable of linear structure Linear resonance extends to increase the charge transfer rate and at the same time has the dipole characteristics of electrons and holes to enhance the conductivity of the ruthenium oligomer.

Based on the foregoing example "A", the method for synthesizing the oligo-oligomer of the present invention can also form oligo-oligomeric molecules of different configurations under the same normal reaction (ie, formula 1), and the oligomeric product thereof The oxime oligomer; as shown in the examples "B" and "C", please refer to the reaction formulas described in Figures 2 and 3 and the text. The operation means here is the same as the previous embodiment, so only the relevant reaction formula is briefly described in the following description, and details are not described again.

"B" 6-bromo-1,4-dimethoxyanthracene (6-bromo-1,4-DMA). The synthesis method consists of the following steps:

a) starting from B with potassium permanganate, pyridine and water, and after the reaction is completed and filtered and concentrated to remove pyridine, an aqueous solution is obtained, and acid water and acetic acid are added to the aqueous solution. The ethyl acetate is reacted again until the compound B1 is produced; as detailed in the reaction formula [B-1].

Wherein, the starting material B of the present embodiment may be 4-bromo-1,2-xylene (4-bromo-o-xylene); and the compound B1 produced is a white solid.

The results of the analysis of the compound B1 are as follows: ¹ H-NMR (300 MHz, d-acetone) δ (ppm): 3.79 (br), 7.72 (d, J = 8.4 Hz, 1H), 7.80 (dd, J =2.1 Hz, J=J=8.4 Hz, 1H), 7.88 (s, 1H); ¹³ C-NMR (75 MHz, d-acetone) δ (ppm): 125.1, 131.4, 132.0, 134.3, 135.6, 167.2, 167.5.

b) using compound B1 together with methylene chloride and acetic anhydride The reaction is carried out until the compound B2 is produced; as detailed in the reaction formula [B-2].

Wherein, the compound B1 is continuously heated to reflux with methylene chloride and acetic anhydride to give a clear transparent liquid, and the acetic anhydride is reacted to form acetic acid; and the compound B2 produced is also white solid as the compound B1. .

The compound B2 was analyzed as follows: ¹ H-NMR (300 MHz, CDCl ₃ ) δ (ppm): 7.87 (d, J = 8.1 Hz, 1H), 8.03 (dd, J = 1.5 Hz, J = 8.1 Hz, 1H), 8.16 (s, 1H); ¹³ C-NMR (75 MHz, CDCl ₃ ) δ (ppm): 126.8, 128.9, 129.8, 131.5, 132.9, 139.3, 161.9.

c) adding compound B2 together with hydroquinone (1,4-dihydroxybenzene) to a reaction mixture mixed with aluminum chloride and sodium chloride, and continuing the reaction until the compound B3 is produced; For example, the reaction formula [B-3].

Among them, the aluminum trichloride and the sodium chloride are first heated in an oil pan of 110 ° C ~ 130 ° C until they are completely melted to form a reaction liquid, before the compound B2 and hydroquinone are added, and the oil temperature is controlled to rise. To 150 ° C; and the compound B3 produced was a red solid.

The results of the analysis of the compound B3 are as follows: ¹ H-NMR (300 MHz, CDCl ₃ ) δ (ppm): 7.34 (s, 2H), 7.94 (dd, J = 1.8 Hz, J = 8.4 Hz, 1H) , 8.20 (d, J = 8.4 Hz, 1H), 8.48 (s, 1H), 12.77 (s, 1H), 12.86 (s, 1H); ¹³ C-NMR (75 MHz, CDCl ₃ ) δ (ppm): 112.4, 112.5, 128.7, 129.6, 129.9, 130.0, 130.2, 132.0, 134.5, 137.5, 158.0, 158.0, 185.5, 186.0.

d) co-reacting with compound B3 with potassium carbonate and acetone, and adding dimethyl sulfate to continue to produce compound B4; as detailed in reaction formula [B-4].

Among them, the compound B4 produced was a yellow solid.

The compound B4 was analyzed as follows: ¹ H-NMR (300 MHz, CDCl3) δ (ppm): 4.00 (s, 6H), 7.37 (s, 2H), 7.81 (dd, J = 1.8 Hz, J = 8.4 Hz, 1H), 8.02 (d, J = 8.4 Hz, 1H), 8.28 (s, 1H); ¹³ C-NMR (75 MHz, CDCl3) δ (ppm): 57.0, 120.3, 120.5, 128.4, 128.7 , 129.4, 132.7, 135.2, 136.4, 154.2, 182.1, 182.6.

e) The compound B4 is placed in an ice bath together with tetrahydrofuran and methanol, and sodium borohydride is added in portions to carry out a reaction to obtain an intermediate product, and the intermediate product is dissolved in a tetrahydrofuran solution, and stannous chloride is added thereto. The reaction yields the compound B5 which is 6-bromo-1,4-dimethoxyanthracene; as detailed in the reaction formula [B-5].

Wherein the intermediate product is a beige solid; the compound B5 is a dark green solid.

Further, the compound B5 was confirmed to be 6-bromo-1,4-dimethoxyanthracene, and the analysis results were as follows: ¹ H-NMR (300 MHz, CDCl ₃ ) δ (ppm): 4.03 (s) , 6H), 6.63 (s, 2H), 7.49 (dd, J = 1.8 Hz, J = 9 Hz, 1H), 7.88 (d, J = 9 Hz, 1H), 8.19 (s, 1H), 8.67 (s, 1H) ), 8.74 (s, 1H); ¹³ C-NMR (75 MHz, CDCl ₃ ) δ (ppm): 55.6, 101.3, 101.6, 119.6, 120.0, 121.1, 125.6, 126.0, 129.0, 129.6, 130.2, 130.3, 132.1 , 149.3, 149.4.

Similarly, 6-bromo-1,4-dimethoxyfluorene with a halogen functional group at a specific position can be obtained via a pro-reaction reaction step, and can be 6-bromo-1,4-dimethoxyanthracene ( That is, the compound B5) is selected as an oligomeric monomer and then subjected to a boronation reaction to form an oligomeric precursor of the oligomerization reaction.

In detail, this embodiment may also be selected after the foregoing step e), and the other step f) is carried out by the boron esterification reaction of the compound B5 to form the compound B6; wherein the detailed steps of the boron esterification reaction are the same as in the preceding examples. The only monomer used is 6-bromo-1,4-dimethoxyfluorene (ie, compound B5), and the same content will not be repeated. For example, the reaction formula [B-6].

The compound B6 was analyzed to confirm that it was an oligomeric precursor of 6-bromo-1,4-dimethoxyanthracene, and the analysis results were as follows: ¹ H-NMR (300 MHz, CDCl ₃ ) δ (ppm) ): 1.36 (s, 12H), 4.01 (s, 3H), 4.02 (s, 3H), 6.55 (d, J = 8.1 Hz, 1H), 6.59 (d, J = 8.1 Hz, 1H), 7.81 (d) , J = 8.4 Hz, 1H), 8.02 (d, J = 8.4 Hz, 1H), 8.63 (s, 1H), 8.77 (s, 1H), 8.86 (s, 1H); ¹³ C-NMR (75 MHz, CDCl ₃ ) δ (ppm): 24.8, 24.9, 55.6, 55.6, 83.9, 100.8, 101.4, 120.4, 122.0, 125.4, 126.2, 127.5, 129.4, 130.8, 132.5, 137.7, 149.3, 149.6.

And when this embodiment obtains the compound B5 and the compound B6, it is also optional The compound B5 and the compound B6 are oligosed to the oxime oligomer B7, which is 5,8-5',8'TMDA; as detailed in the reaction formula [B-7].

Among them, this example is selected to use palladium (II) acetate, 2-dicyclohexylphosphino-2', 6'-dimethoxybiphenyl The compound B5 and the compound B6 are reacted; and the aqueous solution of tetrahydrofuran and potassium phosphate is added, followed by heating, refluxing, extraction and precipitation to obtain a compound B7 which is a yellow solid; at this time, the yield of the compound B7 is about 52%. . And the compound B7 was confirmed to be a quinone dimer molecule 5,8-5',8'TMDA, and the analysis results were as follows: ¹ H-NMR (300 MHz, CDCl ₃ ) δ (ppm): 4.06 (s, 6H), 4.07 (s, 6H), 6.64 (s, 4H), 7.94 (dd, J = 1.8 Hz, J = 8.4 Hz, 2H), 8.16 (d, J = 8.4 Hz, 2H), 8.41 (s, 2H), 8.82 (s, 2H), 8.88 (s, 2H); ¹³ C-NMR (125 MHz, CDCl ₃ ) δ (ppm): 55.7, 101.1, 120.6, 121.3, 125.6, 125.9, 126.4, 129.3, 130.7, 131.8, 137.8, 149.5, 149.6.

"C" 6-bromo-2,3-dimethoxyanthracene (-DMA). The synthesis method consists of the following steps:

a) Compound B2 is co-reacted with vetatrole, anhydrous hydrochloride (dihydrous dichloromethane), and aluminum chloride is added in portions, and the mixture is continuously applied to produce a mixture of compound C1 and compound C1'; Reaction formula [C-1].

b) A mixture containing the compound C1 and the compound C1' is reacted with concentrated sulfuric acid in an oil bath until the compound C2 is produced; as detailed in the reaction formula [C-2].

And the result of the analysis of the compound C2 is as follows: ¹ H-NMR (300 MHz, CDCl ₃ ) δ (ppm): 4.06 (s, 6H), 7.68 (s, 2H), 7.85 (dd, J = 2.1 Hz , J = 8.4 Hz, 1H), 8.10 (d, J = 8.4, 1H), 8.37 (s, 1H); ¹³ C-NMR (75 MHz, CDCl ₃ ) δ (ppm): 56.6, 108.4, 128.0, 128.2 , 128.7, 129.2, 130.0, 132.1, 134.6, 136.7, 153.9, 154.0, 181.3, 181.7.

c) The compound C2 is placed in an ice bath together with tetrafluorofuran and methanol, and sodium borohydride is added in portions to carry out a reaction to obtain an intermediate product C2', and the intermediate product C2' is continuously reacted with tetrafluorofuran. Until it is completely dissolved, stannous chloride is added until the reaction yields compound C3, which is 6-bromo-1,4-dimethoxyanthracene; as detailed in reaction formula [C-3]

Further, the compound C3 was analyzed to be 6-bromo-1,4-dimethoxyanthracene, and the analysis results were as follows: ¹ H-NMR (300 MHz, CDCl ₃ ) δ (ppm): 4.04 (s) , 3H), 4.05 (s, 3H), 7.18 (s, 2H), 7.42 (dd, J = 1.5 Hz, J = 9.0 Hz, 1H), 7.78 (d, J = 9.0 Hz, 1H), 8.11 (s) , 1H), 8.18 (s, 1H); ¹³ C-NMR (75 MHz, CDCl ₃ ) δ (ppm): 55.9, 104.7, 104.8, 118.5, 123.0, 124.2, 128.0, 128.7, 128.9, 129.1, 129.3, 129.3 , 131.5, 150.3, 150.5.

Similarly, 6-bromo-1,4-dimethoxyfluorene with a halogen functional group at a specific position can be obtained via a pro-reaction reaction step, and can be 6-bromo-1,4-dimethoxyanthracene ( That is, the compound C3) is selected as an oligomeric monomer and then subjected to a boronation reaction to form an oligomeric precursor of the oligomerization reaction.

In detail, this embodiment can also be selected after the foregoing step c), and the other step d) is carried out by the boron esterification reaction of the compound C3 to form the compound C4; wherein the detailed steps of the boron esterification reaction are the same as in the preceding examples. The only monomer to be treated is 6-bromo-1,4-dimethoxyanthracene (ie, compound C3), and the same content will not be repeated. For example, the reaction formula [C-4].

The compound C4 was analyzed to confirm that it was an oligomeric precursor of 6-bromo-1,4-dimethoxyanthracene, and the analysis results were as follows: ¹ H-NMR (300 MHz, CDCl ₃ ) δ (ppm) ): 1.41 (s, 12H), 4.05 (s, 3H), 4.06 (s, 3H), 7.19 (s, 1H), 7.21 (s, 1H), 7.72 (d, J = 8.4 Hz, 1H), 7.89 (d, J = 8.4 Hz, 1H), 8.19 (s, 1H), 8.26 (s, 1H), 8.48 (s, 1H); ¹³ C-NMR (75 MHz, CDCl ₃ ) δ (ppm): 24.9, 55.9, 83.9, 104.8, 105.1, 123.7, 125.1, 126.6, 128.5, 128.5, 129.4, 130.2, 132.0, 136.7, 149.9, 150.4.

And based on the technical concept of the same oligomer, the quinone oligomer C5 can also be formed by oligomerization of the compound C3 with the compound C4, and the oxime oligomer C5 is 6,7-6', 7'TMDA (detailed as a reaction) The reaction process of the formula [C-5] is easily accomplished by those skilled in the art in view of the foregoing concept, and the reaction process will not be described again.

It is worth noting that the structure symmetrical to the 6-bromo-1,4-dimethoxyanthracene produced by the synthesis method of the above-mentioned Example "B" is 6-bromo-1,4-dimethoxyanthracene. And the structure symmetrical to the 6-bromo-1,4-dimethoxyanthracene produced by the synthesis method of the above embodiment "C" is 6-bromo-2,3-dimethoxyanthracene. Those skilled in the art can understand, and no further details are provided herein.

In addition to the examples shown in the aforementioned "A", "B", "C", the usual reaction (ie, formula 1) can be used as the main one, and the compound II' is substituted for the compound II to produce a new reaction. Starting material D (detailed in formula 2);

Wherein X is substituted by a halogen functional group, and OR is an alkoxy group and is located at the C9 and C10 positions.

Based on the general reaction formula 2, the present invention can further synthesize the oligomeric molecules of different configurations from the starting material D1; as shown in the example "D", please refer to FIG. 4 and the internal text together. The reaction formula.

"D" 2-bromo-9,10-dimethoxy-anthracene, 2-bromo-9, 10-DMA. The synthesis method consists of the following steps:

a) Compound D1 is co-reacted with ethanol and sodium borohydride, and under the continuous action of potassium hydroxide and dimethyl sulfate, compound D2 is produced, and the compound D2 is 2-bromo-9,10-dimethoxy Basis; as detailed in the reaction formula [D-1].

For example, in this embodiment, another 1.5 grams and 5.2 millimoles of the compound D1 are separately placed in another double-necked flask together with about 15 milliliters of ethanol and about 15 milliliters of water. Sodium borohydride (preferably 1.58 g and 41.6 mmol) is added in portions for about 30 minutes, then an aqueous potassium hydroxide solution (about 3.2 ml and a concentration of about 10 M) and dimethyl sulfate are added. (preferably 1.76 g and 52 mmol), the reaction is continued for 5-8 hours, and then the compound D2 is obtained as a pale yellow solid by extraction, precipitation, etc.; at this time, the yield of the compound D2 is about 25%. . And the compound D2 was analyzed to be 2-bromo-9,10-dimethoxyanthracene, and the analysis results were as follows: ¹ H-NMR (300 MHz, CDCl ₃ ) δ (ppm): 4.11 (s) , 3H), 4.11 (s, 3H), 7.52-7.55 (m, 3H), 8.15 (d, J = 9 Hz), 8.26 (m, 2H), 8.45 (s, 1H); ¹³ C-NMR (75 MHz, CDCl ₃ ) δ (ppm): 63.4, 63.4, 120.1, 122.6, 122.6, 123.04, 124.6, 125.1, 125.6, 125.6, 125.7, 126.0, 128.8, 147.5, 148.8.

Similarly, 2-bromo-9,10-dimethoxyanthracene with a halogen functional group at a specific position can be obtained via a pro-reaction reaction step, and can be 2-bromo-9,10-dimethoxyanthracene ( That is, the compound D2) is selected as an oligomeric monomer and then subjected to a boronation reaction to form an oligomeric precursor of the oligomerization reaction.

In detail, this embodiment may also be selected after the foregoing step a), and the other step b) is carried out by the boron esterification reaction of the compound D2 to form the compound D3; wherein the detailed steps of the boron esterification reaction are the same as in the preceding examples. The only monomer is 2-bromo-9,10-dimethoxyanthracene (ie, compound D2), and the same content will not be repeated. For example, the reaction formula [D-2].

The compound D3 was analyzed to confirm that it was an oligomeric precursor of 2-bromo-9,10-dimethoxyanthracene, and the analysis results were as follows: ¹ H-NMR (300 MHz, CDCl ₃ ) δ (ppm) ): 1.41 (s, 12H), 4.11 (s, 3H), 4.17 (s, 3H), 7.48-7.53 (m, 2H), 7.81 (dd, J = 2.4 Hz, J = 8.7 Hz, 1H), 8.27 (m, 3H), 8.84 (s, 1H); ¹³ C-NMR (75 MHz, CDCl ₃ ) δ (ppm): 24.9, 30.9, 63.1, 63.7, 83.9, 121.4, 122.5, 122.9, 124.3, 124.8, 125.2 , 125.8, 129.3, 131.5, 148.1, 149.5.

And based on the technical concept of the same oligomerization, the ruthenium oligomer D4 can also be formed by oligomerization of the compound D2 with the compound D3, the oxime oligomer D4 is 9,10-9', 10'TMDA; Formula [D-3]. The reaction process of the oxime oligomer D4 is the same as that of the oxime oligomer B7, and can be easily accomplished by those skilled in the art in view of the foregoing concept, and will not be described again.

And the compound D4 was analyzed to confirm that it was a quinone dimer molecule 9,10-9', 10'TMDA, and the analysis results were as follows: ¹ H-NMR (300 MHz, CDCl ₃ ) δ (ppm): 4.19 (s, 6H), 4.21 (s, 6H), 7.52 - 7.55 (m, 4H), 8.00 (dd, J = 1.8 Hz, J = 9 Hz, 2H), 8.32 - 8.36 (m, 4H), 8.45 (d , J=9 Hz, 2H), 8.69 (s, 2H); ¹³ C-NMR (125 MHz, CDCl ₃ ) δ (ppm): 63.4, 120.5, 122.6, 122.7, 123.6, 124.1, 125.1, 125.5, 125.6, 137.7, 148.5.

In summary, the present invention can be obtained by reacting a ruthenium oligomer molecule produced by a prosthetic synthesis method into a monomer and reacting a ruthenium dimer of different configurations such as compounds A5, B7, C5, and D4; The pro-oligomeric oligomeric molecule takes any two configuration as an oligomerization reaction to produce a ruthenium dimer of various configurations according to the following formula 3 based on the same reaction process; see Fig. 5 for each configuration.

Wherein, OR ₁ and OR ₂ may be located at C1, C4, C5, C8, C6, C7 or C9, C10 positions respectively; OR ₃ and OR ₄ may be located at C1, C4, C5, C8, C6, C7 or C9, C10, respectively. Position; and R ₁ , R ₂ , R ₃ , and R ₄ may be one of CH ₃ to C ₂₀ H ₄₁ and H ₂ C.

As shown in Fig. 5, it is a ruthenium dimer based on the structure of the formula III. Among them, (1) 1,4-1', 4'TMDA; (2) 1,4-9,, 10'TMDA; (3) 1,4-5', 8'TMDA; (4) 1, 4 -6', 7'TMDA; (5) 9, 10-9', 10'TMDA; (6) 9, 10-5', 8'TMDA; (7) 9, 10-6', 7'TMDA; (8) 6,7-6',7'TMDA; (9)5,8-5',8'TMDA; (10)5,8-6',7'TMDA; above, with the forefront (1) The ~(10) symmetrical configuration is also intended to be protected by the case, and is mainly based on the three-form configuration, and will not be repeated one by one.

Moreover, the present invention can also be arbitrarily selected by using 2,6-bromo-9,10-dialkylfluorene or 2,6-bromo-9,10-dialkylynyl fluorene as an oligomeric host. The oligomeric molecules are collectively subjected to an oligomerization reaction to produce a trimeric trimer of various configurations such as the following formula IV, and the detailed oligomerization process is identical to the oligomerization reaction described above, and will not be described again; See Figure 6 for the type of triad.

Wherein, OR ₁ and OR ₂ may be located at C1, C4, C5, C8, C6, C7 or C9, C10 positions respectively; OR ₃ and OR ₄ may be located at C1, C4, C5, C8, C6, C7 or C9, C10, respectively. And R ₁ , R ₂ , R ₃ , and R ₄ may be one of CH ₃ to C ₂₀ H ₄₁ and H ₂ C; and R ₅ and R ₆ may be CH ₃ to C ₂₀ H ₄₁ , H ₂ CC ≡C~C ₂₀ H ₂₁ -C≡C One of them.

As shown in Fig. 6, it is based on a ruthenium dimer composed of the three structures. Among them, (1) 1,4-9", 10"-1', 4'TMTA; (2) 1,4-9", 10"-9', 10'TMDA; (3) 1,4-9 ", 10"-5', 8'TMDA; (4) 1,4-9", 10"-6', 7'TMDA; (5) 9, 10-9", 10"-9', 10' TMDA; (6) 9, 10-9", 10"-5', 8'TMDA; (7) 9, 10-9", 10"-6', 7'TMDA; (8) 6, 7-9 ", 10"-6', 7'TMDA; (9) 5, 8-9", 10"-5', 8'TMDA; (10) 5, 8-9", 10"-6', 7' TMDA; above, its configuration relative to the preceding (1) ~ (10) is also the protection of the case, only the four-type configuration, not repeated one by one.

In summary, the method for synthesizing a ruthenium oligomer molecule of the present invention can not only perform a substitution reaction at a specific position of a ruthenium molecule (ie, carbon No. 2 or No. 6), but also complete a specific structural modification, and more specifically The modified ruthenium monomer is used as an oligomerization reaction, so that the oligo-formed ruthenium dimer or ruthenium trimer can be linear; thus, the linear structure of the ruthenium oligomer system can have a better resonance extension to enhance The charge transfer rate, and at the same time, the dipole characteristics of the electrons and holes that it has, further enhance the conductivity of the ruthenium oligomer.

While the invention has been described in connection with the preferred embodiments described above, it is not intended to limit the scope of the invention. The technical scope protected by the invention, and thus the present invention The scope of protection is subject to the definition of the scope of the patent application attached.

Claims (16)

A method for synthesizing a ruthenium oligomer molecule, which comprises the following reactions: Wherein X is H, OR is alkoxy and is at the C1, C4 position; or X is a halogen functional group and is at C6, OR is an alkoxy group and is at the C1, C4 position; or X is a halogen functional group, and OR is an alkane Oxyl and located at the C2, C3 position; or X is H, W is a halogen functional group and is located at C2, OR is an alkoxy group and is located at the C1, C4 positions. The method for synthesizing an oligomeric molecule according to the first aspect of the patent application, wherein the 2-bromo-1,4-dimethoxyanthracene of the formula (A3) is prepared, The method comprises the steps of: a) co-reacting with starting material A with potassium carbonate, acetone and dimethyl sulfate until compound A1 is produced; b) the compound A1 is placed in an ice bath together with tetrahydrofuran and methanol, and sodium borohydride is added in portions to carry out a reaction to obtain an intermediate product A1', and the intermediate product A1' is continuously reacted with tetrafluorofuran to the same. Completely dissolved, adding stannous chloride until the reaction yields compound A2; c) The reaction of the compound A2 with N-bromosuccinimide and dichloromethane until the compound A3 is produced, which is 2-bromo-1,4-dimethoxyfluorene. The method for synthesizing an oligomeric molecule according to the second aspect of the patent application, further comprising d) performing a boronation reaction with the compound A3 to form a compound A4. The method for synthesizing an oligomeric molecule according to the third aspect of the patent application, wherein the compound A3 is coupled with the compound A4 to a terpene dimer A5 which is 1,4-1', 4' TMDA . The method for synthesizing an oligomeric molecule according to the first aspect of the patent application, wherein the 6-bromo-1,4-dimethoxyanthracene for preparing the formula (B5) comprises the following steps: The method comprises the steps of: a) reacting starting material B with potassium permanganate, pyridine and water, and after the reaction is completed, filtering and concentrating to remove pyridine, an aqueous solution is obtained, and acid water and ethyl acetate are added to the aqueous solution. Extracting and purifying to obtain compound B1; b) co-reacting with compound B1 with dichloromethane and acetic anhydride until compound B2 is produced; c) the compound B2 is added together with hydroquinone in a reaction mixture mixed with aluminum trichloride and sodium chloride, and the reaction is continued until the compound B3 is produced; d) co-reacting with compound B3 with potassium carbonate, acetone, and adding dimethyl sulfate to continue to produce compound B4; e) The compound B4 is placed in an ice bath together with tetrahydrofuran and methanol, and sodium borohydride is added in portions to carry out a reaction to obtain an intermediate product, and the intermediate product is dissolved in a tetrahydrofuran solution, and stannous chloride is added. Until the reaction yields the compound B5, the compound B5 is 6-bromo-1,4-dimethoxyanthracene. The method for synthesizing an oligomeric molecule according to item 5 of the patent application, further comprising f) performing a boronation reaction with the compound B5 to form a compound B6. The method for synthesizing an oligomeric molecule according to the sixth aspect of the patent application, wherein the compound B5 and the compound B6 are oligomerized to a ruthenium oligomer B7, and the ruthenium oligomer B7 is 5,8-5',8' TMDA. The method for synthesizing an oligomeric molecule according to the first aspect of the patent application, wherein the 6-bromo-1,4-dimethoxyanthracene for preparing the formula (C3) comprises the following steps: The method comprises the steps of: a) co-reacting compound B2 with phthalic acid, anhydrous dichloromethane, and adding aluminum chloride in portions, and continuing to act to produce a mixture of compound C1 and compound C1'; b) reacting a mixture containing the compound C1 and the compound C1' with concentrated sulfuric acid in an oil bath until the compound C2 is produced; c) The compound C2 is placed in an ice bath together with tetrahydrofuran and methanol, and sodium borohydride is added in portions to carry out a reaction to obtain an intermediate product C2', and the intermediate product C2' is dissolved in a tetrahydrofuran solution and added. Stannous chloride until the reaction yields compound C3, which is 6-bromo-2,3-dimethoxyindole. The method for synthesizing an oligomeric molecule according to the second aspect of the patent application, further comprising d) performing a boronation reaction with the compound C3 to form a compound C4. The method for synthesizing an oligomeric molecule according to Item 9 of the patent application, wherein the compound C3 and the compound C4 are oligomerized to a ruthenium oligomer C5, which is 6,7-6', 7' TMDA. A method for synthesizing a ruthenium oligomer molecule, which comprises the following reactions: Wherein X is substituted by a halogen functional group, and OR is an alkoxy group and is located at the C9 and C10 positions. The method for synthesizing an oligomeric molecule according to Item 11 of the patent application, wherein the 2-bromo-9,10-dimethoxyanthracene for preparing the formula (D2) comprises the following steps: The method comprises the steps of: a) co-reacting compound D1 with ethanol and sodium borohydride, and under the continuous action of potassium hydroxide and dimethyl sulfate, producing compound D2, which is 2-bromo-9. 10-dimethoxyanthracene. The method for synthesizing an oligomeric molecule according to claim 12, further comprising b) performing a boronation reaction with the compound D2 to form a compound D3. The method for synthesizing an oligomeric molecule according to Item 13 of the patent application, wherein the compound D2 and the compound D3 are oligomerized to a ruthenium oligomer D4, which is 9,10-9', 10' TMDA. A quinone oligomer, such as the following structural formula: Wherein, OR ₁ and OR ₂ may be located at C1, C4, C5, C8, C6, C7 or C9, C10 positions respectively; OR ₃ and OR ₄ may be located at C1, C4, C5, C8, C6, C7 or C9, C10, respectively. Position; and R ₁ , R ₂ , R ₃ , and R ₄ may be one of CH ₃ to C ₂₀ H ₄₁ and H ₂ C. A quinone oligomer, such as the following structural formula: Wherein, OR ₁ and OR ₂ may be located at C1, C4, C5, C8, C6, C7 or C9, C10 positions respectively; OR ₃ and OR ₄ may be located at C1, C4, C5, C8, C6, C7 or C9, C10, respectively. And R ₁ , R ₂ , R ₃ , and R ₄ may be one of CH ₃ to C ₂₀ H ₄₁ and H ₂ C; and R ₅ and R ₆ may be CH ₃ to C ₂₀ H ₄₁ , H ₂ CC ≡C~C ₂₀ H ₂₁ -C≡C One of them.