Preparation method of aromatic acene derivative and hetero-acene derivative

Abstract

The invention belongs to the technical field of organic synthesis, and discloses a preparation method of an aromatic acene derivative and a hetero-acene derivative. # imgabs0 is used for heating and reacting a compound 3 shown in the formula with MLm'and RCN in an organic solvent, so as to prepare a target product. According to the method, a substituent group is introduced to the tail end of a planar molecule with a pi electron skeleton and more than three rings, and an acetylene equivalent is selected to realize the trimerization reaction of alkynes. Different from acetylene, the method has no explosiveness, can be used for synthesis under mild conditions, and is convenient for industrial safety application, so that the method is very suitable for being popularized and applied as a synthesis means.

Description

Technical Field

[0001] The present invention belongs to the technical field of organic synthesis and relates to a method for preparing aromatic acene derivatives and heteroacene derivatives, and in particular to a method for synthesizing aromatic acene derivatives and heteroacene derivatives by utilizing acetylene equivalents. Background Art

[0002] Organic semiconductors have attracted attention because currently used semiconductors, such as silicon, are hard and insoluble in organic solvents. Unlike hard, solid silicon, organic semiconductors, thought to be soluble in organic solvents, began to surpass amorphous silicon in 1997 with the emergence of pentacene, a member of a family of organic compounds known as acenes. The chemical formulas for acenes are shown below: anthracene with three rings, tetracene with four, and pentacene with five. These compounds are called "acenes" because they contain "acene."

[0003] As organic semiconductor materials, their solubility gradually deteriorates as aromatic compounds condense. Without the introduction of substituents such as alkyl groups, they become insoluble in organic solvents, hindering their full potential for printing and inkjet printing. Taking pentacene derivatives as an example, organic semiconductor materials like pentacene can be modified to incorporate appropriate substituents, making them easily soluble in organic solvents. Semiconductors can be easily integrated into circuits using printing or inkjet printing, and their potential applications are expected to expand significantly, for example, enabling the manufacture of televisions through printing and the integration of screens into flexible items such as clothing.

[0004] Another major challenge with organic semiconductor materials is that they require a π-electron molecule in the basic skeleton. To achieve the high mobility required for semiconductors, it is crucial that the π orbitals of two or more planar π-electron molecules overlap, forming a so-called π-stacking structure. Therefore, if larger substituents are added, the overlapping planar molecules will separate, preventing high performance. Therefore, it is important to avoid introducing large substituents at positions that would interfere with molecular overlap. However, in the synthesis of such compounds, it is currently difficult to introduce the desired substituents onto the aromatic skeleton of linear organic semiconductor materials. The most convenient method is trimerization of alkynes, but if a -CH=CH- structure is to be added to the terminus, acetylene must be used. To avoid the use of explosive acetylene, there is an urgent need to design and synthesize a method for synthesizing aromatic acene derivatives and heteroacene derivatives using acetylene equivalents. Summary of the Invention

[0005] Based on the current state of the art, the present invention aims to provide a method for synthesizing aromatic acene derivatives and heteroacene derivatives using acetylene equivalents that can replace acetylene.

[0006] To achieve the purpose of the present invention, after unremitting efforts, we have systematically introduced arbitrary substituents on each aromatic ring of acene derivatives for the first time. Taking pentacene derivatives as an example, by introducing substituents, pentacene derivatives can be completely soluble in organic solvents, such as Figure 1 As shown in Figure 1. On the left, pentacene is placed in chloroform, where particles can be seen floating without dissolving. In contrast, pentacene with introduced alkyl substituents dissolves well in chloroform, forming a dark blue solution.

[0007] The following are examples of acene derivatives and heteroacene derivatives that exhibit high-performance organic semiconductors:

[0008] From the perspective of organic semiconductors showing high performance, it is known that substituents such as organic groups for improving solubility are placed in a position away from the central ring to avoid interfering with the π stacking of the aromatic ring condensed into a chain. In addition, when introducing alkyl groups at both ends, it is also not easy to introduce, so there are great limitations in terms of synthesis. In this sense, compounds with a constituent of more than three planar π electron systems and substituents at both ends are expected to play an important role in the future, so their synthesis method is particularly important. And the present application can well achieve its safe synthesis at normal temperature and pressure.

[0009] The synthetic route of the present invention is as follows: Existing technology The present invention The present invention adopts MLm' complex as acetylene equivalent to replace acetylene to carry out trimerization reaction and synthesize aromatic acene derivatives and heteroacene derivatives.

[0010] Wherein, M represents a metal of Group 3 to Group 5 of the Periodic Table of Elements or the lanthanide series, preferably titanium, zirconium or hafnium; L is its ligand, which is a nonlocalized cyclic η 5-coordination ligand, more preferably cyclopentadienyl or substituted cyclopentadienyl, indenyl or substituted indenyl, fluorenyl or substituted fluorenyl, azulenyl or substituted azulenyl. The substituted cyclopentadienyl group includes methylcyclopentadienyl, ethylcyclopentadienyl, isopropylcyclopentadienyl, tert-butylcyclopentadienyl, dimethylcyclopentadienyl, diethylcyclopentadienyl, diisopropylcyclopentadienyl, di-tert-butylcyclopentadienyl, and tetramethylcyclopentadienyl; the substituted indenyl group includes 2-methylindenyl, 2-methyl-4-phenylindenyl, tetrahydroindenyl, and benzoindenyl; the substituted fluorenyl group includes benzofluorenyl, tetrahydrofluorenyl, and octahydrofluorenylmethyl. In addition, two or more nonlocal cyclic η 5 -coordinated ligands, such as cyclopentadienyl groups, can also be crosslinked via one or more cyclic crosslinking groups. Examples of crosslinking groups include CH2, CH2CH2, CH(CH3)CH2, CH(C4H9)C(CH3)2, C(CH3)2, (CH3)2Si, (CH3)2Ge, (CH3)2Sn, (C6H5)2Si, (C6H5)(CH3)Si, (C6H5)2Ge, (C6H5)2Sn, (CH2)4Si, CH2Si(CH3)2, o-C6H4, or 2, 2'-(C6H4)2.

[0011] When three or more aromatic rings, such as benzene or thiophene rings, are condensed, they function as organic semiconductors. This is because, upon forming the aromatic rings, alkyne substituents are also introduced. However, if too many substituents are introduced, π stacking of the organic semiconductor molecular rings will not occur, and the semiconductor function will be reduced. To achieve this, an unsubstituted -CH=CH- moiety must be added to the aromatic rings. The synthetic method of the present invention achieves this goal. Where R 1 、R 2 and R are the same or different and are independently a hydrogen atom or a C1-C12 atom optionally having a substituent including a halogen atom. 40 Hydrocarbon group; C1 to C2 optionally having a substituent containing a halogen atom 40 Alkoxy; C6 to C6 optionally having a substituent containing a halogen atom 40 an aryloxy group; an amine group; a hydroxyl group or an alkoxy group, a silyl group or a substituted silyl group, a stannyl group, a boryl group, or an aromatic group. m', m, n, p, q, and r are all integers from 0 to 5.

[0012] The target compound is obtained by heating the compound 3 of the above formula with MLm' and RCN in an organic solvent.

[0013] In the formula, preferably, R1 、R 2 and R are the same or different and are independently a hydrogen atom, a silyl group or a phenyl group. The silyl group is preferably a trimethylsilyl group, a dimethylphenylsilyl group, a methyldiphenylsilyl group, a triphenylsilyl group, a dimethylethylsilyl group, a methylmethoxyphenylsilyl group, a methylethylphenoxysilyl group or the like. More preferably, R1 and R2 are the same or different and are independently hydrogen or trimethylsilyl; R is selected from phenyl; m' is 1; m, n, p, q, and r are all 0; M is titanium or zirconium; and the ligand L is a cyclopentadienyl group.

[0014] Advantages of this method include introducing substituents at the termini of planar molecules with a π-electron backbone and three or more rings, using acetylene equivalents, to achieve trimerization of alkynes. Unlike acetylene, this method is non-explosive and can be synthesized under mild conditions, making it safe for industrial application. Therefore, this method is highly suitable for widespread application as a synthetic method. BRIEF DESCRIPTION OF THE DRAWINGS

[0015] Figure 1 This is a photo of pentacene derivatives dissolved in organic solvents. DETAILED DESCRIPTION In order to better illustrate the present invention, the following examples are given:

[0016] According to one embodiment of the present invention, examples of silyl groups that can be used in practicing the present invention are not limited and include trimethylsilyl, dimethylphenylsilyl, methyldiphenylsilyl, triphenylsilyl, dimethylethylsilyl, methylmethoxyphenylsilyl, and methylethylphenoxysilyl. Examples of the boryl group useful in the practice of the present invention include, but are not limited to, dialkylboryl groups, pinacolboryl groups, diphenylboryl groups, and the like.

[0017] M chooses titanium.

[0018] L represents a cyclopentadienyl group.

[0019] The reaction is preferably carried out in a temperature range of -100° C. to 300° C., particularly preferably in a temperature range of -80° C. to 100° C., and more preferably in a temperature range of -50° C. to 50° C. The pressure is, for example, in a range of 0.1 bar to 2500 bar, preferably in a range of 0.5 bar to 10 bar.

[0020] As the solvent, an aliphatic or aromatic organic solvent can be used. Examples of the solvent include ether solvents such as tetrahydrofuran or diethyl ether; halogenated hydrocarbons such as dichloromethane; halogenated aromatic hydrocarbons such as o-dichlorobenzene; amides such as N,N-dimethylformamide, sulfoxides such as dimethyl sulfoxide; and aromatic hydrocarbons such as benzene, toluene, and xylene.

[0021] The present invention will now be described with reference to Examples, but the present invention is not limited to the following Examples.

[0022] All reactions were carried out under a nitrogen atmosphere. THF, ether, hexane, and benzene used as solvents were distilled to anhydrous state using sodium metal and benzophenone under a nitrogen stream, and 1,2-dichloroethane was distilled using phosphorus pentoxide under nitrogen pressure. Zirconocene dichloride and titanocene dichloride were purchased from Aldrich Chemical Company, Inc. and Nichia Chemical Industry Co., Ltd. Other reagents were purchased from Kanto Chemical, Tokyo Chemical Industry, and Aldrich, respectively. Measurements were made using a Bruker ARX-400 or a JEOL JNM-LA300. 1 H-NMR and 13 C-NMR spectrum. The internal standard used was 1 H-NMR: tetramethylsilane; 13 C-NMR: deuterated chloroform. Gas chromatography analysis was performed using a Shimadzu GC-14A gas chromatograph equipped with a Shimadzu UCBP1-M25-025 fused silica capillary column, and data were recorded using a Shimadzu CR6A-Chromatopac integrator. When determining yields by GC, mesitylene and n-dodecane were used as internal standards. Column chromatography was performed using Kanto Chemical Silica Gel 60N (spherical, neutral), 40-100 μm.

[0023] Example 1

[0024] (1) Preparation of compound 4 Under nitrogen atmosphere, compound 3 of the above formula was dissolved in tetrahydrofuran organic solvent, MLm' and RCN were added and heated at 50°C for reaction to obtain compound 4.

[0025] (2) 1,4-Bis(trimethylsilyl)-5,10-dihydroanthracene derivative (Compound 5) was synthesized from 1,4-bis(cyclopentadienyl)-2,9-bis(trimethylsilyl)-2,8-titanatecyclopentadiene derivative (Compound 4). Place a 20mL Schlenk tube under nitrogen, and then place 0.3mmol of compound 4 into the Schlenk tube. Add 3.6mL of toluene thereto and stir at 80°C for 24 hours. Cool it to 40°C, remove the solvent, and add 3.6mL of xylene at room temperature. Add 0.6mmol (61.6μl) of benzonitrile thereto and heat at 115°C for 36 hours. The reaction solution is treated with an aqueous sodium bicarbonate solution, and the organic matter is extracted with ethyl acetate. After washing the organic layer with water and brine, remove the solvent of the organic layer. Purify by silica gel column chromatography using a 5:1 mixture of hexane:ethyl acetate. After removing the solvent, the target compound 5 is obtained with a yield of 75%. 1 H NMR (400 MHz, CDCl3): 1 HNMR: δ0.39 (s, 18H), 3.99 (s, 4H), 7.19 (m, 2H), 7.28 (m, 2H), 7.36 (m, 2H). 13 C{ 1 H} NMR (101MHz, C6D6): δ0.15, 37.6, 126.1, 126.1, 126.5, 131.3, 137.8, 138.6, 138.8, 142.6.

Claims

1. A method for preparing aromatic acene derivatives and heteroacene derivatives, characterized in that: This is achieved through the following steps: Where R 1 、R 2 and R are the same or different and are independently a hydrogen atom or a C1-C40 hydrocarbon group optionally having a substituent containing a halogen atom; a C1-C40 alkoxy group optionally having a substituent containing a halogen atom; a C6-C40 aryloxy group optionally having a substituent containing a halogen atom; an amino group; a hydroxyl group or an alkoxy group, a silyl group or a substituted silyl group, a stannyl group, a boryl group or an aromatic group; m', m, n, p, q, and r are all integers from 0 to 5; in addition, in the formula, M is a metal of Group 3, Group 4 or Group 5, and L is its ligand; the L ligand is a cyclopentadienyl group or a substituted cyclopentadienyl group, an indenyl group or a substituted indenyl group, a fluorenyl group or a substituted fluorenyl group, an azulenyl group or a substituted azulenyl group.

2. The method for preparing aromatic acene derivatives and heteroacene derivatives according to claim 1, wherein: Where R 1 、R 2 and R are the same or different and are independently: a hydrogen atom or a trimethylsilyl group, a dimethylphenylsilyl group, a methyldiphenylsilyl group, a triphenylsilyl group, a dimethylethylsilyl group, a methylmethoxyphenylsilyl group or a methylethylphenoxysilyl group or a phenyl group; m', m, n, p, q, r are all integers from 0 to 5; M is titanium, zirconium or hafnium; and the L ligand is a cyclopentadienyl group or a methylcyclopentadienyl group, an ethylcyclopentadienyl group, an isopropylcyclopentadienyl group, a tert-butylcyclopentadienyl group, a dimethylcyclopentadienyl group, a diethylcyclopentadienyl group, a diisopropylcyclopentadienyl group, a di-tert-butylcyclopentadienyl group or a tetramethylcyclopentadienyl group.

3. The method for preparing aromatic acene derivatives and heteroacene derivatives according to claim 2, wherein: R 1 、R 2 The same or different, respectively and independently are: hydrogen atom or trimethylsilyl; R is selected from phenyl; m' is 1; m, n, p, q, r are all 0; M is titanium or zirconium; L ligand is cyclopentadienyl.

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