CN112961025A - Synthesis method, derivation method and derivatives of non-benzene polycyclic aromatic hydrocarbon APD - Google Patents

Synthesis method, derivation method and derivatives of non-benzene polycyclic aromatic hydrocarbon APD Download PDF

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CN112961025A
CN112961025A CN202110314088.4A CN202110314088A CN112961025A CN 112961025 A CN112961025 A CN 112961025A CN 202110314088 A CN202110314088 A CN 202110314088A CN 112961025 A CN112961025 A CN 112961025A
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apd
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benzene
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王小野
刘鹏才
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Nankai University
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Abstract

The invention discloses a synthesis method of a non-benzene polycyclic aromatic hydrocarbon APD, which comprises the following steps: (1) coupling reaction, namely reacting 5, 6-disubstituted acenaphthene or acenaphthylene, a C4 synthon, a transition metal catalyst, a ligand and alkali in a solvent to obtain a compound B; (2) and (3) carrying out dehydrogenation reaction, namely heating the compound B and an oxidant in a solvent to react to obtain a product. The method efficiently synthesizes APD through a two-step method, the total yield is up to more than 44%, gram-level synthesis of APD can be realized, and a foundation is laid for further research and derivatization of the APD; the invention also provides a derivatization method of the APD, which synthesizes a key compound containing bromine through the bromination of the APD, lays a foundation for subsequent coupling, ring closing and other derivatization reactions, synthesizes a series of substituted APD derivatives with novel and diversified structures through derivatization design, and synthesizes a series of organic conjugated molecules with diversified structures and taking the APD as a core through pi expansion.

Description

Synthesis method, derivation method and derivatives of non-benzene polycyclic aromatic hydrocarbon APD
Technical Field
The invention relates to the field of polycyclic aromatic hydrocarbon synthesis, in particular to a synthesis method, a derivation method and derivatives of non-benzene polycyclic aromatic hydrocarbon APD.
Background
In recent years, Polycyclic Aromatic Hydrocarbons (PAHs) have attracted extensive research interest in the fields of chemistry, physics and material science due to their potential application values in the fields of organic photoelectric functional materials, nano-graphene and the like. The non-benzene type (containing non-six-membered aromatic rings) polycyclic aromatic hydrocarbons can be used for constructing pi-expanded non-benzene type Nano Graphene (NGs) with unique electronic and magnetic properties due to unique physicochemical properties of the non-benzene type polycyclic aromatic hydrocarbons.
Azulene, as an isomer of naphthalene, is a typical non-benzene polycyclic aromatic hydrocarbon, has the characteristics of large dipole moment, small band gap and the like, and has been successfully applied to the fields related to photoelectricity and energy sources as an important component at present. APD (acelleidylene) is taken as an isomer of pyrene, and has the characteristics of larger dipole moment, smaller band gap and the like. Their structural formulae are compared as follows:
Figure BDA0002991060930000011
APD was first synthesized by Boekelheide et al in 1956 (Boekelheide, V.; Vick, G.K.A Synthesis of pleiadine and acelleidylene. J.Am.chem.Soc.1956,78, 653-. The synthetic route is as follows: starting from acenaphthene, acenaphthene (1) is first Friedel-Crafts reacted with succinic anhydride to produce beta- (1-acenaphthenyl) -propionic acid (2a), and it is noted that this reaction inevitably produces a regioisomeric by-product (beta- (1-acenaphthenyl) -propionic acid) (2b), making separation and purification difficult. The compound beta- (1-acenaphthenyl) -propionic acid (2a) obtained by the reaction is esterified to obtain a compound 3. Melting NaCl-AlCl in compound 33The second Friedel-Crafts reaction in (1) to form a seven-membered ring, i.e., Compound 4 can be obtained in 43% yield. Compound 4 can then be reduced to compound 5 in 77% yield and compound 6 can be obtained in 46% yield by elimination. Finally, dehydrogenation of compound 6 under Pd/C conditions gave APD in 20% yield. The synthesis route starts from acenaphthene (1), and APD is obtained through 6 steps of reaction, and the total yield is only 2.4%. The reaction process is as follows:
Previous synthetic route to APD(Boekelheide et al.,1956)
Figure BDA0002991060930000021
wherein the reaction conditions are as follows: (i) succinic anhydride, aluminum chloride, nitrobenzene, 0 ℃; (ii) heating methanol and concentrated sulfuric acid; (iii) sodium chloride, aluminum chloride, 150 ℃; (iv) refluxing lithium aluminum hydride and benzene; (v) hydrochloric acid, ethanol, room temperature; (vi) palladium on carbon, mesitylene, reflux.
In conclusion, the APD and the derivatives thereof have certain research and application values in the fields of non-benzene polycyclic aromatic hydrocarbons, non-benzene nano graphene and the like. However, the existing synthesis method has the problems of complicated steps, harsh reaction conditions, low yield and the like, and greatly limits the application and development of the APD and the derivatives thereof, so that the development of a simple and efficient synthesis route of the APD and the derivatives thereof has important significance.
Disclosure of Invention
In order to solve the problems in the prior art, the invention aims to provide a synthesis method of non-benzene polycyclic aromatic hydrocarbon APD, which has simple process, mild reaction conditions and high yield;
it is another object of the present invention to provide a method for preparing substituted APD derivatives from APD;
it is a further object of the present invention to provide certain substituted APD derivatives;
it is still another object of the present invention to provide a non-benzene-type polycyclic aromatic compound having APD as a core skeleton.
Therefore, the technical scheme of the invention is as follows:
a synthetic method of non-benzene polycyclic aromatic hydrocarbon APD comprises the following steps:
(1) compound 8 was prepared by a coupling reaction, the reaction scheme and procedure were as follows:
Figure BDA0002991060930000022
adding 1 equivalent of reactant 7, 1 to 4 equivalents of C4 synthon, 0.01 to 0.5 equivalent of transition metal catalyst, 0 to 0.5 equivalent of ligand, 0 to as long as5 equivalents of a base in the solvent S1Medium heating to temperature T1Carrying out reaction for 4-24 hours to obtain a compound 8,
wherein the reactant 7 is 5, 6-disubstituted acenaphthene or acenaphthylene, and the substituent X is chlorine, bromine or iodine;
the C4 synthon is a compound having the structure:
Figure BDA0002991060930000031
the transition metal catalyst is selected from palladium acetate, palladium chloride, tetratriphenylphosphine palladium, ditriphenylphosphine palladium dichloride, 1' -bisdiphenylphosphine ferrocene palladium dichloride, tris (dibenzylideneacetone) dipalladium or 1, 3-bis (diphenylphosphine) propane nickel dichloride;
the ligand is selected from 2-dicyclohexylphosphine-2 ',6' -dimethoxy-biphenyl, triphenylphosphine, tricyclohexylphosphine, tricresylphosphine, 1' -bisdiphenylphosphinoferrocene or 4, 5-bisdiphenylphosphine-9, 9-dimethylxanthene;
the alkali is selected from potassium phosphate aqueous solution, potassium carbonate aqueous solution, sodium hydroxide aqueous solution, triethylamine, diisopropylethylamine or pyridine;
the solvent S1And corresponding temperature T1Respectively dichloromethane at 25-40 ℃; tetrahydrofuran, 25-70 ℃; 1, 4-dioxane, 25-100 ℃; toluene, 25-120 ℃; benzene, 25-80 ℃; straight chain alkane of C5-C10, 25-boiling point; 1, 3-dimethyl-3, 4,5, 6-tetrachloro-2 (1H) pyrimidinone, 25-180 ℃;
the concentration C1As a reaction product in a solvent S1In the range of 0.1mM to 2M;
the dotted line in the structures of the reactants and products represents a carbon-carbon single bond or a carbon-carbon double bond;
(2) APD was prepared by dehydrogenation, the equation and reaction sequence were as follows:
Figure BDA0002991060930000032
adding 1 equivalent of the compound prepared in the step (1) and 8, 3-10 equivalents of oxidant into a reaction bottle, and adding the mixture into a solvent S2Medium heating to temperature T2Carrying out reaction for 4-24 hours to obtain a product APD,
wherein the reactant of the step is the product of the step (1);
the oxidant is selected from benzoquinone, 2,3,5, 6-tetrachlorobenzoquinone, 2, 3-dichloro-5, 6-dicyano-1, 4-benzoquinone, manganese dioxide or benzoyl peroxide;
the solvent S2And corresponding temperature T2Comprises the following steps: dichloromethane, 25-40 ℃; 1, 2-dichloroethane, 25-80 ℃; tetrahydrofuran, 25-70 ℃; 1, 4-dioxane at 25-100 ℃); toluene, 25-120 ℃; benzene, 25-80 ℃; xylene, 25-130 ℃; 25-165 ℃ of mesitylene; straight chain alkane of C5-C10, 25-boiling point; 25-85 ℃ of carbon tetrachloride.
The concentration C2As a reactant in a reaction solvent S2In the range of 0.1mM to 2M.
Preferably, the reaction auxiliary agent in the step (2) further comprises an additive, the addition amount of the additive is 3-10 equivalents, the additive is selected from potassium tert-butoxide, sodium tert-butoxide, potassium carbonate, potassium phosphate, acetic acid, trifluoroacetic acid, trifluoromethanesulfonic acid or silica gel, and the additive is preferably potassium tert-butoxide.
Preferably, in the step (1), the reactant 7 is 3, 4-dibromoacenaphthylene (7a) or 3, 4-dibromoacenaphthylene (7 b); the transition metal catalyst is palladium acetate or palladium chloride; the ligand is 2-dicyclohexyl phosphine-2 ',6' -dimethoxy biphenyl or triphenylphosphine; the alkali is potassium phosphate or triethylamine; the solvent S1Is tetrahydrofuran or toluene.
Preferably, in the step (2), the oxidizing agent is 2, 3-dichloro-5, 6-dicyano-1, 4-benzoquinone, manganese dioxide or benzoyl peroxide; the solvent S2Toluene, benzene, or carbon tetrachloride.
The present invention provides a process for the preparation of substituted APD derivatives from APDs comprising the steps of:
(1) bromo-cyclohepta [ fg ] acenaphthylene (9) is prepared by bromination, the reaction formula and reaction process are as follows:
Figure BDA0002991060930000041
adding 1 equivalent of compound APD, 1-4 equivalents of bromine source and 0-4 equivalents of auxiliary agent into a reaction bottle, and adding the mixture into a solvent S3Medium heating to temperature T3Reacting for 4-24 hours to obtain the compound bromo cyclohepta [ fg]An acenaphthylene (9),
wherein the content of the first and second substances,
the bromine source is a compound capable of providing bromine atoms or bromine positive ions and comprises liquid bromine, N-bromosuccinimide, phenyltrimethyl ammonium tribromide or dibromohydantoin;
the auxiliary agent is a compound capable of promoting bromine free radicals or bromine positive ions to generate, and comprises benzoyl peroxide, ferric trichloride or acetic acid;
the solvent S3And corresponding temperature T3Comprises the following steps: dichloromethane, 25-40 ℃; 1, 2-dichloroethane, 25-80 ℃; tetrahydrofuran, 25-70 ℃; 1, 4-dioxane at 25-100 ℃); toluene, 25-120 ℃; benzene, 25-80 ℃; xylene, 25-130 ℃; 25-165 ℃ of mesitylene; 25-180 ℃ of chlorobenzene; n, N-dimethylformamide at 25-150 ℃; methanol, 25-70 ℃; ethanol, 25-80 ℃; dimethyl sulfoxide, 25-160 ℃;
said temperature T3Is higher than solvent S3Melting point lower than solvent S3The temperature of the boiling point;
the concentration C3As a reactant in a reaction solvent S3In the range of 0.1mM to 2M;
the product 9 is substituted by dibromine or monobromine;
(2) compound 10 was prepared by a transition metal coupling reaction, the reaction scheme and procedure were as follows:
Figure BDA0002991060930000051
adding 1 equivalent of the compound 9a prepared in the step (1), 0.01-0.2 equivalent of a transition metal catalyst and 2-4 equivalents of a fragment containing an R group into a reaction bottle, and dissolving the mixture in a solvent S4Medium heating to temperature T4Carrying out reaction for 4-24 hours to obtain a product 10,
wherein the transition metal catalyst is selected from palladium acetate, palladium tetratriphenylphosphine and palladium ditriphenylphosphine dichloride;
the R group-containing segment is selected from cuprous cyanide, zinc cyanide, carbon monoxide, a substituted or unsubstituted aryl or heteroaryl containing boronic acid, a tin reagent, a Grignard reagent, or a zinc reagent;
the additive is selected from triphenylphosphine, diadamantyl butyl phosphine, 2-dicyclohexylphosphine-2 ',6' -dimethoxy-biphenyl, alkylamine of C1-C10, sodium tert-butoxide, potassium tert-butoxide, 1, 8-diazabicycloundecen-7-ene or potassium phosphate;
the solvent S4And corresponding temperature T4Comprises the following steps: dichloromethane, 25-40 ℃; 1, 2-dichloroethane, 25-80 ℃; tetrahydrofuran, 25-70 ℃; 1, 4-dioxane, 25-100 ℃; toluene, 25-120 ℃; benzene, 25-80 ℃; xylene, 25-130 ℃; 25-165 ℃ of mesitylene; straight chain alkane of C5-C10, 25-boiling point; n, N-dimethylformamide at 25-140 ℃; 25-160 ℃ of N, N-dimethylacetamide;
the concentration C4As a reactant in a reaction solvent S4The concentration of (A) is in the range of 0.01M-0.5M;
preferably, the R group in step (2) is any one of the following:
Figure BDA0002991060930000052
the obtained product is any one of the following products:
Figure BDA0002991060930000061
preferably, the transition metal catalyst is palladium acetate; the R group-containing segment is a boronic acid, tin reagent, grignard reagent, or zinc reagent containing a substituted or unsubstituted aryl or heteroaryl group; the additive is 2-dicyclohexylphosphine-2 ',6' -dimethoxy-biphenyl and potassium phosphate; the solvent is tetrahydrofuran.
A substituted APD derivative having the general formula:
Figure BDA0002991060930000062
wherein R is1、R2、R3、R4、R5、R6、R7、R8、R9And R10Is hydrogen, halogen or cyano, or is optionally substituted aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, alkyl, cycloalkyl, alkoxy, aryloxy, heteroaryloxy, arylthio, heteroarylthio or alkyl-substituted silicon, where R is1～R10Not hydrogen at the same time.
Preferably, R is2～R9Are each hydrogen, said substituted APD derivative having any of the following structures:
Figure BDA0002991060930000071
a non-benzene polycyclic aromatic compound having APD as a core skeleton, having the following general formula (4):
Figure BDA0002991060930000072
wherein rings A, B, C, D, E, F, G, H, I, J are each independently hydrogen, an aromatic ring group or a heteroaromatic ring group, which rings cannot both be hydrogen,
X1、X2、X3、X4、X5、X6、X7、X8、X9and X10Each independently hydrogen, halogen or cyano, or an aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, alkyl, cycloalkyl, alkoxy, aryloxy, heteroaryloxy, arylthio, heteroarylthio or alkyl-substituted silicon group which may be substituted.
Preferably, the non-benzene polycyclic aromatic compound has any one of the following structures:
Figure BDA0002991060930000081
the invention has the following beneficial effects:
1. the synthesis method of the non-benzene polycyclic aromatic hydrocarbon APD efficiently synthesizes the APD through a two-step method, the total yield of the APD is up to more than 44%, gram-level synthesis of the APD can be realized, and a foundation is laid for further research and derivatization of the APD;
2. the invention provides a derivatization method of APD for the first time, namely, a key compound containing bromine is synthesized through bromination of APD, so that subsequent derivatization such as coupling, ring closing and the like can be carried out;
3. the invention synthesizes a series of substituted APD derivatives with novel and diversified structures through the derivatization design of APD.
4. The invention synthesizes a series of organic conjugated molecules which take APD as a core and have diversified structures through the pi expansion of the APD.
Detailed Description
The method of the present invention will be described in detail with reference to specific examples. Abbreviations and Chinese names for the compounds in the examples are as follows:
THF: tetrahydrofuran; 9-BBN: 9-borabicyclo (3,3,1) -nonane; pd (OAc)2: palladium acetate;
SPhos: 2-dicyclohexylphosphine-2 ',6' -dimethoxybiphenyl; hexane: n-hexane; DCM: dichloromethane;
MeOH: methanol; DDQ: 2, 3-dichloro-5, 6-dicyanobenzoquinone; t-BuOK: potassium tert-butoxide;
NBS: n-bromosuccinimide; PE: petroleum ether; TfOH: trifluoromethanesulfonic acid; DBH: dibromohydantoin.
The synthesis method of the APD comprises two steps: (I) coupling reaction; and (II) dehydrogenation reaction.
Meanwhile, the invention firstly provides derivatization of APD and designs and synthesizes a series of derivatives with diversified structures. The derivatives have the following general formula:
Figure BDA0002991060930000091
in the formula R1-R10Is hydrogen, halogen or cyano, or is optionally substituted aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, alkyl, cycloalkyl, alkoxy, aryloxy, heteroaryloxy, arylthio, heteroarylthio or alkyl-substituted silicon, these radicals not simultaneously being hydrogen
In addition, the invention also provides pi expansion of APD, and designs and synthesizes a series of non-benzene polycyclic aromatic hydrocarbons with diversified structures, wherein the structures of the non-benzene polycyclic aromatic hydrocarbons are shown as the following formula:
Figure BDA0002991060930000092
in the formula Ar1-Ar6All are various common aromatic rings (benzene ring, biphenyl), multiple aromatic rings (such as naphthalene, anthracene, phenanthrene, etc.), and heteroaromatic rings (such as thiophene, indole, furan, pyridine, carbazole, etc.).
R1And R2C1-C10 straight-chain or branched-chain alkenyl, alkynyl, mono-substituted or multi-substituted phenyl, mono-substituted or multi-substituted polyaromatic ring group, mono-substituted or multi-substituted heteroaromatic ring (thiophene, indole, furan, pyridine, carbazole and the like substituted at different positions), and the position of the substituent can be any substitutable position of the compound.
The compounds, derivatives and processes for the preparation of the compounds and derivatives of the present invention will be described in detail below with reference to examples.
First, the coupling reaction in the APD synthesis reaction will be described:
example 1a
A method for preparing 1,2,5,6,7, 8-hexahydrocyclohepta [ fg ] acenaphthene (8a) by coupling reaction, which has the following reaction formula and reaction process:
Figure BDA0002991060930000101
first, 1, 3-butadiene (19.2mL,38.4mmol,2.0M in THF) and 9-borabicyclo (3,3,1) -nonane (154.0mL,76.8mmol,0.5M in THF) were added to a Schlenk flask and the reaction stirred at room temperature for 24h to prepare borane.
To another Schlenk bottle was added palladium acetate (717.0mg,3.2mmol), 2-dicyclohexylphosphine-2 ',6' -dimethoxybiphenyl (2.63g,6.4mmol), potassium phosphate (20.40g,96.0mmol) and 3, 4-dibromoacenaphthylene (formula 7a,10.00g,32.0mmol), followed by tetrahydrofuran (270mL), water (50mL) and the freshly prepared borane under argon atmosphere, stirred at 70 ℃ for 2h and cooled to room temperature.
Thereafter, the mixture obtained after the reaction was extracted with ethyl acetate and the organic phases were combined, washed with water and a saturated sodium chloride solution, respectively, and dried over anhydrous magnesium sulfate. Concentrating and spin-drying the organic phase, and using normal hexane for the obtained crude product: dichloromethane 100: 1 on a silica gel column and recrystallized from dichloromethane/methanol to give finally white solid 8a (5.32g, yield 80%).1H NMR(300MHz,CD2Cl2,297K,ppm)δ7.10(s,4H),3.31(s,4H), 3.18(m,4H),2.04(m,4H).13C NMR(75MHz,CD2Cl2,297K,ppm)δ144.55,141.21,137.94, 132.10,127.73,119.42,33.21,30.57,27.91.HRMS(EI)m/z:Calcd.for C16H16:208.1252；Found: 208.1245M+.
Example 1b
A method for preparing 1,2,5,6,7, 8-hexahydrocyclohepta [ fg ] acenaphthene (8a) by coupling reaction, which has the following reaction formula and reaction process:
Figure BDA0002991060930000102
1, 3-butadiene (19.2mL,38.4mmol,2.0M in THF) and tri-n-butylstannane (22.3g,76.8mmol) were added to a Schlenk flask and the reaction stirred at room temperature for 24h to prepare stannane.
To another Schlenk bottle was added palladium chloride (566.4mg,3.2mmol), triphenylphosphine (1.68g,6.4mmol), triethylamine (9.79g,96.0mmol) and 3, 4-dibromoacenaphthylene (formula 7a,10.00g,32.0mmol), followed by toluene (270mL) and the above fresh stannane under an argon atmosphere. The mixture was stirred at 110 ℃ for 12h and cooled to room temperature. The mixture was extracted with ethyl acetate and the organic phases were combined, washed with water and saturated sodium chloride solution, respectively, and dried over anhydrous magnesium sulfate. Concentrating and spin-drying the organic phase, and carrying out reaction on the obtained crude product with n-hexane: dichloromethane 100: 1 on a silica gel column and recrystallized from dichloromethane/methanol to give finally white solid 8a (4.79g, 72%).
Example 1c
A preparation method of a compound 8b has the following reaction formula and reaction process:
Figure BDA0002991060930000111
first, 1, 3-butadiene (19.2mL,38.4mmol,2.0M in THF) and 9-borabicyclo (3,3,1) -nonane (154.0mL,76.8mmol,0.5M in THF) were added to a Schlenk flask and the reaction stirred at room temperature for 24h to prepare borane.
To another Schlenk bottle was added palladium acetate (717.0mg,3.2mmol), 2-dicyclohexylphosphine-2 ',6' -dimethoxybiphenyl (2.63g,6.4mmol), potassium phosphate (20.40g,96.0mmol) and 3, 4-dibromoacenaphthylene (formula 7b,10.00g,32.0 mmol), followed by tetrahydrofuran (270mL), water (50mL) and the freshly prepared borane above under an argon atmosphere. The mixture was stirred at 70 ℃ for 2h and cooled to room temperature.
Then, the mixture obtained after the reaction was extracted with ethyl acetate and the organic phases were combined,the organic phase was washed with water and saturated sodium chloride solution, respectively, and dried over anhydrous magnesium sulfate. Concentrating and spin-drying the organic phase, and using normal hexane for the obtained crude product: dichloromethane 100: 1 on a silica gel column and recrystallized from dichloromethane/methanol to give finally 8b (5.32g, 80%) as an orange solid.1H NMR(300MHz,CD2Cl2,297K,ppm)δ1H NMR(400MHz, Chloroform-d)δ7.59(dd,J＝6.9,1.9Hz,1H),7.31(d,J＝6.9Hz,1H),7.05(d,J＝2.2Hz,1H), 3.21(q,J＝3.7,3.2Hz,2H),2.01(q,J＝3.1Hz,2H).13C NMR(75MHz,CD2Cl2,297K,ppm)δ 144.55,141.21,138.62,137.94,132.10,127.73,119.42,30.57,27.91.HRMS(EI)m/z:Calcd.for C16H16:206.1252；Found:206.1245M+.
Example 1d
Figure BDA0002991060930000112
To a Schlenk bottle were added 3, 4-dibromoacenaphthene (structural formula 7a,3.12g,10.0mmol),1, 3-bis (diphenylphosphino) propanenickel dichloride (271.0mg,0.5mmol), and tetrahydrofuran (50mL), and 1, 4-magnesium dibromide butane (1M, 12mL) was added dropwise. After the addition was complete, the mixture was stirred at 70 ℃ for 10h and cooled to room temperature. The mixture was extracted with ethyl acetate and the organic phases were combined, washed with water and saturated sodium chloride solution, respectively, and dried over anhydrous magnesium sulfate. Concentrating and spin-drying the organic phase, and carrying out reaction on the obtained crude product with n-hexane: dichloromethane 100: 1 on a silica gel column and recrystallized from dichloromethane/methanol to give finally white solid 8a (1.07g, 52%).
Example 1e
Figure BDA0002991060930000121
To a Schlenk bottle were added 3, 4-dibromoacenaphthylene (structural formula 7b,3.12g,10.0mmol), tris (dibenzylideneacetone) dipalladium (458.2mg,0.5mmol), and tetrahydrofuran (50mL), and 1, 4-zinc dichloride butane (1M, 12mL) was added dropwise. After the addition was complete, the mixture was stirred at 70 ℃ for 10h and cooled to room temperature. The mixture was extracted with ethyl acetate and the organic phases were combined, washed with water and saturated sodium chloride solution, respectively, and dried over anhydrous magnesium sulfate. Concentrating and spin-drying the organic phase, and carrying out reaction on the obtained crude product with n-hexane: dichloromethane 100: 1 on a silica gel column and recrystallized from dichloromethane/methanol to give finally 8a (0.99g, 48%) as an orange solid.
(II) the dehydrogenation reaction in the APD synthesis reaction is described below:
example 2a
A method for preparing non-benzene polycyclic aromatic hydrocarbon (APD) through dehydrogenation reaction comprises the following reaction formula and reaction process:
Figure BDA0002991060930000122
to a Schlenk bottle was added compound 8a prepared in example 1a (2.80g,13.4mmol) and 2, 3-dichloro-5, 6-dicyanobenzoquinone (DDQ, 18.34g,80.6mmol), potassium tert-butoxide (t-BuOK, 15.08g,134.5mmol), toluene (260mL, 0.05M). The mixture was stirred at 80 ℃ for 17h and cooled to room temperature to give a crude product, which was supplemented with 2, 3-dichloro-5, 6-dicyanobenzoquinone (6.10g,26.88mmol), potassium tert-butoxide (15.08g,134.48mmol) and toluene (260mL, 0.05M), stirred at 80 ℃ for 4h and cooled to room temperature. The resulting mixture was then filtered through celite, the filtrate was concentrated and spin dried to give a crude product which was purified using n-hexane: dichloromethane 100: 1 on a silica gel column to finally obtain APD (1.54g, yield 55%) as a red solid.1H NMR(300MHz,CD2Cl2,297K,ppm)δ8.38(d, J＝7.4Hz,1H),7.99(d,J＝7.4Hz,1H),7.89(s,1H),7.81(dt,J＝8.8,4.1Hz,1H),6.96(dt,J＝ 8.9,4.1Hz,1H).13C NMR(75MHz,CD2Cl2,297K,ppm)δ138.46,137.36,135.06,127.77, 127.45,127.42,126.75,126.45,126.31.HRMS(EI)m/z:Calcd.for C16H16:208.1252；Found: 208.1245M+.
Example 2b
A method for preparing non-benzene polycyclic aromatic hydrocarbon (APD) through dehydrogenation reaction comprises the following reaction formula and reaction process:
Figure BDA0002991060930000131
to a Schlenk bottle was added compound 8a prepared in example 1a (2.08g,10mmol), manganese dioxide (6.96g,80 mmol), and toluene (20mL, 0.5M). And (2) stirring the mixture at 25 ℃ for reaction for 48h, filtering and separating solids in a system by using kieselguhr, and spin-drying the filtrate to obtain a crude product, wherein the reaction is carried out by using n-hexane: dichloromethane 100: 1 on a silica gel column to finally obtain APD (586mg, 29%) as a red solid.
Example 2c
A method for preparing non-benzene polycyclic aromatic hydrocarbon (APD) through dehydrogenation reaction comprises the following reaction formula and reaction process:
Figure BDA0002991060930000132
to a Schlenk bottle was added compound 8b prepared in example 1b (2.06g,10mmol), benzoyl peroxide (7.26g, 30mmol), and carbon tetrachloride (50mL, 0.2M). And (2) stirring the mixture at 80 ℃ for reaction for 12h, filtering and separating solids in a system through diatomite, and carrying out spin drying on the filtrate to obtain a crude product, wherein the reaction is carried out by using normal hexane: dichloromethane 100: 1 on a silica gel column to finally obtain APD (247mg, 12%) as a red solid.
The following examples illustrate the preparation of substituted APD derivatives from APD in detail. The method comprises two steps: (1) bromo-cyclohepta [ fg ] acenaphthylene (compound 9) is prepared through bromination reaction; (2) substituted APD derivatives are prepared by transition metal coupling reactions.
The process for the preparation of bromocyclohepta [ fg ] acenaphthylene (compound 9) by bromination is first described:
example 3a
A method for preparing bromocyclohepta [ fg ] acenaphthylene (compound 9) has the following reaction formula and reaction process:
Figure BDA0002991060930000141
first, APD (600mg,2.97mmol), tetrahydrofuran (6mL,0.5M) and then N-bromosuccinimide (1.12g,6.24mmol) were added to a single vial, and the reaction was stirred at 25 ℃ for 12 h. The reaction was then quenched by addition of water, and the resulting mixture was extracted with dichloromethane and the organic phases were combined, washed with water and saturated sodium chloride solution, respectively, and dried over anhydrous magnesium sulfate. Concentrating and spin-drying the organic phase, and carrying out reaction on the obtained crude product with n-hexane: dichloromethane ═ 30: 1 on a silica gel column and recrystallized from dichloromethane/methanol to give finally 9a as a red solid (705.7mg, 66%).1H NMR(300MHz,CD2Cl2,297K,ppm)δ8.31(d,J＝7.6Hz,1H),8.00(d,J＝7.6Hz,1H),7.85 (dt,J＝8.8,4.2Hz,1H),7.08(dq,J＝8.3,4.5Hz,1H).13C NMR(75MHz,CD2Cl2,297K,ppm)δ 139.51,137.79,131.73,128.89,127.88,126.61,125.26,124.75,116.94.HRMS(EI)m/z:Calcd. for C16H8Br2:358.8972；Found:359.8966M+. And red solid 9b (70.7mg, 7%).1H NMR(300MHz, CD2Cl2,297K,ppm)δ8.41(d,J＝7.5Hz,1H),8.32(d,J＝7.5Hz,1H),8.01(dd,J＝11.1,7.5Hz, 2H),7.83(d,J＝12.1Hz,2H),7.77(s,1H),7.09–6.94(m,2H).HRMS(EI)m/z:Calcd.for C16H8Br:278.8972；Found:279.8966M+.
Example 3b
A method for preparing bromocyclohepta [ fg ] acenaphthylene (compound 9) has the following reaction formula and reaction process:
Figure BDA0002991060930000142
to a single-necked flask were added APD (600mg,2.97mmol), dichloromethane (6mL,0.5M), followed by liquid bromine (1.02g,6.24mmol) at 0 ℃. The mixture was stirred at 25 ℃ for 12 h. The reaction was then quenched by addition of saturated sodium bisulfite, the aqueous phase was extracted with dichloromethane, the organic phases were combined, washed with water and saturated sodium chloride solution, respectively, and dried over anhydrous magnesium sulfate. Concentrating and spin-drying the organic phase, and carrying out reaction on the obtained crude product with n-hexane: dichloromethane ═ 30: 1 on a silica gel column and recrystallized from dichloromethane/methanol to give finally red solid 9a (556.0mg, 52%) and red solid 9b (55.1mg, 5%).
Example 3c
A method for preparing bromocyclohepta [ fg ] acenaphthylene (compound 9) has the following reaction formula and reaction process:
Figure BDA0002991060930000151
after APD (600mg,2.97mmol) and DBH (1.70g, 6.0mmol) were added to a single vial, acetic acid (6mL,0.5M) was dissolved and reacted at 80 ℃ for 2 h. Then cooled to room temperature, the reaction was quenched by addition of saturated sodium bisulfite, the aqueous phase was extracted with dichloromethane, the organic phases were combined, washed with water and saturated sodium chloride solution, respectively, and dried over anhydrous magnesium sulfate. Concentrating and spin-drying the organic phase, and carrying out reaction on the obtained crude product with n-hexane: dichloromethane ═ 30: 1 on a silica gel column and recrystallized from dichloromethane/methanol to give finally red solid 9a (556.0mg, 52%) and red solid 9b (64.3mg, 6%).
The following detailed description of the process for the preparation of substituted APD derivatives 10 from 1, 2-dibromocyclohepta [ fg ] acenaphthylene (compound 9a) by transition metal coupling reaction:
example 4a
A general synthetic method for preparing 1, 2-disubstituted APD (compound 10 g-10 u) comprises the following reaction formula and reaction process:
Figure BDA0002991060930000152
to a Schlenk bottle was added compound 9a (200mg,0.56mmol), boric acid (1.33mmol), palladium acetate (12.6mg,0.056 mmol), 2-dicyclohexylphosphine-2 ',6' -dimethoxybiphenyl (46mg,0.112mmol), potassium phosphate (357mg,1.68mmol), followed by tetrahydrofuran (11mL), water (1.1mL) under an argon atmosphere. The mixture was stirred at 70 ℃ for 16h and cooled to room temperature. The mixture was extracted with dichloromethane and the organic phases were combined, washed with water and saturated sodium chloride solution, respectively, and dried over anhydrous magnesium sulfate. Concentrating and spin-drying the organic phase, separating and purifying the obtained crude product by using a silica gel column, and recrystallizing by using dichloromethane/methanol to finally obtain the target product.
Example 4b
A general synthetic method for preparing 1, 2-disubstituted APD (compound 10 g-10 u) comprises the following reaction formula and reaction process:
Figure BDA0002991060930000161
to a Schlenk bottle was added compound 9a (200mg,0.56mmol), tin reagent (1.33mmol), palladium chloride (10.1mg, 0.056mmol), triphenylphosphine (29mg,0.112mmol), followed by toluene (11 mL). The mixture was stirred at 100 ℃ for 16h and cooled to room temperature. The mixture was extracted with dichloromethane and the organic phases were combined, washed with water and saturated sodium chloride solution, respectively, and dried over anhydrous magnesium sulfate. Concentrating and spin-drying the organic phase, separating and purifying the obtained crude product by using a silica gel column, and finally obtaining the target product.
Example 4c
A general synthetic method for preparing 1, 2-disubstituted APD (compound 10 g-10 u) comprises the following reaction formula and reaction process:
Figure BDA0002991060930000162
to a Schlenk bottle was added compound 9a (200mg,0.56mmol), Grignard reagent (1.33mmol), 1, 3-bis (diphenylphosphino) propanenickel dichloride (30.1mg,0.056mmol), followed by tetrahydrofuran (11 mL). The mixture was stirred at 70 ℃ for 12h and cooled to room temperature. The mixture was extracted with dichloromethane and the organic phases were combined, washed with water and saturated sodium chloride solution, respectively, and dried over anhydrous magnesium sulfate. Concentrating and spin-drying the organic phase, separating and purifying the obtained crude product by using a silica gel column, and finally obtaining the target product.
Example 4d
A general synthetic method for preparing 1, 2-disubstituted APD (compound 10 g-10 u) comprises the following reaction formula and reaction process:
Figure BDA0002991060930000163
to a Schlenk flask was added compound 9a (200mg,0.56mmol), zinc reagent (1.33mmol), tris (dibenzylideneacetone) dipalladium (45.8mg,0.05mmol), followed by tetrahydrofuran (11 mL). The mixture was stirred at 60 ℃ for 12h and cooled to room temperature. The mixture was extracted with dichloromethane and the organic phases were combined, washed with water and saturated sodium chloride solution, respectively, and dried over anhydrous magnesium sulfate. Concentrating and spin-drying the organic phase, separating and purifying the obtained crude product by using a silica gel column, and finally obtaining the target product.
In examples 4a-4d, the R group in the R group-containing fragment and reaction product is any of the following:
Figure BDA0002991060930000171
correspondingly, the products of examples 4a-4d are one of the following list:
Figure BDA0002991060930000172
representative data for compound 10k, among others, are as follows:
compound 10k, red solid.1H NMR(400MHz,CD2Cl2,297K,ppm)δ8.37(d,J＝7.5Hz,1H), 8.00(d,J＝7.5Hz,1H),7.77(dd,J＝8.7,3.7Hz,1H),7.60–7.53(m,2H),7.46–7.40(m,2H), 7.39–7.33(m,1H),6.94(dd,J＝8.8,3.6Hz,1H).13C NMR(101MHz,CD2Cl2,297K,ppm)δ 137.93,136.55,135.84,135.46,133.66,130.70,128.20,127.35,127.04,126.91,126.65,126.05, 125.11.HRMS(MALDI)m/z:Calcd.for C28H18:354.1409；Found:354.1403M+.
Example 4e
A process for preparing compound 10v, the reaction scheme and procedure are as follows:
Figure BDA0002991060930000181
to a Schlenk bottle was added 9a (100mg,0.28mmol), palladium acetate (156mg,0.56mmol), sodium tert-butoxide (80mg, 0.83mmol) and toluene (5.0mL) under an argon atmosphere. The mixture was slowly warmed to 110 ℃ and stirred for 12h and cooled to room temperature. The mixture was extracted with dichloromethane and the organic phases were combined, washed with water and saturated sodium chloride solution, respectively, and dried over anhydrous magnesium sulfate. Concentrating and spin-drying the organic phase, and carrying out reaction on the obtained crude product with n-hexane: dichloromethane 10: 1 on a silica gel column and recrystallized from dichloromethane/methanol to give finally 10v (89mg, 63%) of a red solid.1H NMR(300MHz,CD2Cl2,297K,ppm)δ8.55(d,J＝6.2Hz,4H)8.44(d,J＝7.2Hz,2H), 8.41(d,J＝7.2Hz,2H),7.94(d,J＝6.2Hz,4H),7.90(dt,J＝8.8,4.2Hz,2H),7.62(dq,J＝8.3, 4.5Hz,2H),7.35(t,J＝6.2Hz,4H),7.16(t,J＝6.2Hz,4H).13C NMR(75MHz,CD2Cl2,297K, ppm)δ145.2,138.7,134.8,131.3,128.2,127.2,126.7,126.6,126.4,125.2,121.4,120.3,119.8, 109.5.HRMS(APCI)m/z:Calcd.for C40H24N2:532.1939；Found:532.1942M+.
Example 4f
A method for preparing 1, 2-dicyan cycloheptene [ fg ] acenaphthylene (compound 10d) comprises the following steps:
Figure BDA0002991060930000182
to a Schlenk bottle was added 9a (200mg,0.56mmol), cuprous cyanide (200mg,2.24mmol), palladium tetrakis triphenylphosphine (57mg, 0.05mmol) under an argon atmosphere and N-methylpyrrolidone (2.8 mL). The mixture was slowly warmed to 160 ℃ and stirred for 16h and cooled to room temperature. The mixture was extracted with dichloromethane and the organic phases were combined, washed with water and saturated sodium chloride solution, respectively, and dried over anhydrous magnesium sulfate. Concentrating and spin-drying the organic phase, and carrying out reaction on the obtained crude product with n-hexane: dichloromethane 10: 1 on a silica gel column and recrystallized from dichloromethane/methanol to give a violet solid 10d (89mg, 63%).1H NMR(300MHz,CD2Cl2,297K,ppm)δ8.44(d,J＝7.2 Hz,1H),8.44(d,J＝7.2Hz,1H),7.90(dt,J＝8.8,4.2Hz,1H),7.62(dq,J＝8.3,4.5Hz,1H).13C NMR(75MHz,CD2Cl2,297K,ppm)δ139.51,137.79,131.73,128.89,127.88,126.61,125.26, 124.75,117.64,116.94.HRMS(EI)m/z:Calcd.for C16H8Br2:252.0687；Found:252.0682M+.
Compounds of the following structure may also be prepared by this method:
Figure BDA0002991060930000191
example 4g
A method for preparing N1, N2-dihexylcyclohepta [ fg ] acenaphthylene-1, 2-diamide (compound 10e) and 8-hexyl-7 hydrocyclohepta [5,6] acenaphthylene-pyrrolin-7, 9(8H) diketone (compound 10f) has the following reaction formula and reaction process:
Figure BDA0002991060930000192
to a Schlenk bottle was added 9a (36mg,0.1mmol), palladium acetate (2.2mg,0.01mmol), and diamantadinePhenylphosphorus (7.2mg,0.02mmol), carbon monoxide was replaced, followed by addition of 1, 8-diazabicycloundecen-7-ene (60 μ L), n-hexylamine (32 μ L) and toluene (1 mL). The mixture was stirred at 110 ℃ for 16h and cooled to room temperature. The mixture was extracted with dichloromethane and the organic phases were combined, washed with water and saturated sodium chloride solution, respectively, and dried over anhydrous magnesium sulfate. Concentrating and spin-drying the organic phase, and carrying out reaction on the obtained crude product with n-hexane: dichloromethane 10: 1 on a silica gel column and recrystallized from dichloromethane/methanol to give a blue solid 10e (9mg, 25%)1H NMR(400MHz, Chloroform-d)δ8.88(d,J＝7.7Hz,1H),8.25(d,J＝7.8Hz,1H),8.19(dd,J＝8.5,3.8Hz,1H), 7.43(dd,J＝8.6,3.7Hz,1H),3.76(t,J＝7.3Hz,1H),1.77(s,1H),1.55(s,1H),1.43(d,J＝7.5 Hz,2H).13C NMR(75MHz,CD2Cl2,297K,ppm)δ177.22,134.84,131.31,128.30,128.04, 127.26,126.63,126.49,125.22,125.02,39.92,30.23,31.55,22.74,14.10.HRMS(ESI)m/z:Calcd. for C24H21NO2:355.1572；Found:356.1577[M+H]+. And purple solid 10f (16mg, 36%)1H NMR (400MHz,Chloroform-d)δ8.67(d,J＝7.6Hz,1H),8.21(s,1H),7.83(d,J＝7.4Hz,1H),7.76 (dd,J＝8.8,3.7Hz,1H),7.10–7.01(m,1H),3.57(d,J＝6.8Hz,2H),1.74(p,J＝7.2Hz,3H), 1.54–1.43(m,3H),1.38(dt,J＝7.4,3.6Hz,5H),0.97–0.88(m,4H).13C NMR(75MHz,CD2Cl2, 297K,ppm)δ175.12,136.88,134.21,129.03,128.41,127.86,126.31,126.01,125.88,124.46, 40.52,31.33,30.10,22.41,14.66.HRMS(ESI)m/z:Calcd.for C30H37N2O2:456.2777；Found: 457.2774[M+H]+。
Example 5
A preparation method of a compound 11a has the following reaction formula and reaction process:
Figure BDA0002991060930000201
to a Schlenk bottle was added compound 10k (100mg,0.28mmol), 2, 3-dichloro-5, 6-dicyanoP-phenylenediamine (384mg, 1.69mmol) and methylene chloride (140mL) and the system was cooled to-78 ℃. Subsequently, trifluoromethanesulfonic acid (7mL) was added to the above mixture, and the reaction was stirred at-78 ℃ for 9h, followed by gradually returning to room temperature and quenching with saturated sodium bisulfite solution. The mixture was extracted with dichloromethane and the organic phases were combined, washed with water and saturated sodium carbonate solution, respectively, and dried over anhydrous magnesium sulfate. The organic phase was concentrated and spin dried and the crude product obtained was purified by distillation with petroleum ether/dichloromethane 10: 1 on a silica gel column and recrystallized from dichloromethane/methanol to give compound 11a (183mg, 52%) as a red solid.1H NMR(400MHz,CDCl3,297K,ppm)δ9.19(d,J＝8.1Hz,1H),9.04(d,J＝ 7.7Hz,1H),8.89(d,J＝8.2Hz,1H),7.91(d,J＝7.6Hz,1H),7.82(t,J＝7.5Hz,1H),7.75(t,J＝ 7.6Hz,1H),7.57(dd,J＝8.9,3.8Hz,1H),6.75(dd,J＝8.9,3.6Hz,1H).13C NMR(101MHz, CDCl3,297K,ppm)δ138.03,137.05,132.40,130.79,130.57,130.50,130.06,129.08,128.00, 127.22,127.12,126.14,126.06,125.27,123.76.HRMS(MALDI)m/z:Calcd.for C28H16:352.1252； Found:352.1251M+.
The following structural compounds can also be prepared by this method:
Figure BDA0002991060930000211
example 6
A preparation method of a compound 11l comprises the following reaction formula and reaction process:
Figure BDA0002991060930000212
to a Schlenk bottle was added compound 9(94mg,0.26mmol), bis- (1, 5-cyclooctadiene) nickel (143mg, 0.520mmol), 1, 5-cyclooctadiene (81mg,0.52mmol),2, 2' -bipyridine (56mg,0.52mmol, 64. mu.L) in a glove box, followed by 1, 4-dioxane (2.6 mL). The mixture was stirred at 70 ℃ for 16h and cooled to room temperature.The mixture was filtered and the resulting solid was washed successively with 50mL of water, 50mL of methanol, 50mL of tetrahydrofuran, 50mL of dichloromethane and 50mL of carbon disulfide to give 11l (36mg, 69%) of a black solid.1H NMR(400MHz,CD2Cl2/CS2,297K,ppm) δ9.41(d,J＝7.6Hz,6H),7.94(d,J＝7.5Hz,6H),7.50–7.42(m,6H),6.66–6.59(m,6H). HRMS(MALDI)m/z:Calcd.for C48H24:600.1878；Found:600.1875M+.
The non-benzene-type polycyclic aromatic compounds prepared in examples 3a, 4b, 4c, 5, and 6 can be used for manufacturing materials for organic photoelectric devices, such as materials for organic electroluminescent devices, materials for organic field effect transistors, and materials for organic solar cells.
The non-benzene-type polycyclic aromatic compounds prepared in examples 3a, 4b, 4c, 5, and 6 are mainly applied to an organic field effect transistor, and the device structure includes a source electrode, a drain electrode, a gate electrode, a dielectric layer, and an active layer, which is prepared by the non-benzene-type polycyclic aromatic compounds prepared in examples 3a, 4b, 4c, 5, and 6 according to the conventional method.

Claims (10)

1. A synthetic method of non-benzene polycyclic aromatic hydrocarbon APD comprises the following steps:
(1) compound 8 was prepared by a coupling reaction, the reaction scheme and procedure were as follows:
Figure FDA0002991060920000011
adding 1 equivalent of reactant 7, 1 to 4 equivalents of C4 synthon, 0.01 to 0.5 equivalent of transition metal catalyst, 0 to 0.5 equivalent of ligand and 0 to 5 equivalents of alkali into a reaction bottle in turn, and dissolving the mixture in a solvent S1Medium heating to temperature T1Carrying out reaction for 4-24 hours to obtain a compound 8,
wherein the reactant 7 is 5, 6-disubstituted acenaphthene or acenaphthylene, and the substituent X is chlorine, bromine or iodine;
the C4 synthon is a compound having the structure:
Figure FDA0002991060920000012
the transition metal catalyst is selected from palladium acetate, palladium chloride, tetratriphenylphosphine palladium, ditriphenylphosphine palladium dichloride, 1' -bisdiphenylphosphine ferrocene palladium dichloride, tris (dibenzylideneacetone) dipalladium or 1, 3-bis (diphenylphosphine) propane nickel dichloride;
the ligand is selected from 2-dicyclohexylphosphine-2 ',6' -dimethoxy-biphenyl, triphenylphosphine, tricyclohexylphosphine, tricresylphosphine, 1' -bisdiphenylphosphinoferrocene or 4, 5-bisdiphenylphosphine-9, 9-dimethylxanthene;
the alkali is selected from potassium phosphate aqueous solution, potassium carbonate aqueous solution, sodium hydroxide aqueous solution, triethylamine, diisopropylethylamine or pyridine;
the solvent S1And corresponding temperature T1Respectively dichloromethane at 25-40 ℃; tetrahydrofuran, 25-70 ℃; 1, 4-dioxane, 25-100 ℃; toluene, 25-120 ℃; benzene, 25-80 ℃; straight chain alkane of C5-C10, 25-boiling point; 1, 3-dimethyl-3, 4,5, 6-tetrachloro-2 (1H) pyrimidinone, 25-180 ℃;
the concentration C1As a reaction product in a solvent S1In the range of 0.1mM to 2M;
the dotted line in the structures of the reactants and products represents a carbon-carbon single bond or a carbon-carbon double bond;
(2) APD was prepared by dehydrogenation, the equation and reaction sequence were as follows:
Figure FDA0002991060920000013
adding 1 equivalent of the compound prepared in the step (1) and 8, 3-10 equivalents of oxidant into a reaction bottle, and adding the mixture into a solvent S2Medium heating to temperature T2Carrying out reaction for 4-24 hours to obtain a product APD,
wherein the reactant of the step is the product of the step (1);
the oxidant is selected from benzoquinone, 2,3,5, 6-tetrachlorobenzoquinone, 2, 3-dichloro-5, 6-dicyano-1, 4-benzoquinone, manganese dioxide or benzoyl peroxide;
the solvent S2And corresponding temperature T2Comprises the following steps: dichloromethane, 25-40 ℃; 1, 2-dichloroethane, 25-80 ℃; tetrahydrofuran, 25-70 ℃; 1, 4-dioxane at 25-100 ℃); toluene, 25-120 ℃; benzene, 25-80 ℃; xylene, 25-130 ℃; 25-165 ℃ of mesitylene; straight chain alkane of C5-C10, 25-boiling point; 25-85 ℃ of carbon tetrachloride;
the concentration C2As a reactant in a reaction solvent S2In the range of 0.1mM to 2M.
2. The method of synthesis according to claim 1, characterized in that: the reaction auxiliary agent in the step (2) comprises an additive, the addition amount of the additive is 3-10 equivalents, the additive is selected from potassium tert-butoxide, sodium tert-butoxide, potassium carbonate, potassium phosphate, acetic acid, trifluoroacetic acid, trifluoromethanesulfonic acid or silica gel, and the preferred additive is potassium tert-butoxide.
3. The method of synthesis according to claim 1, characterized in that: in the step (1), the reactant 7 is 3, 4-dibromoacenaphthylene (7a) or 3, 4-dibromoacenaphthylene (7 b); the transition metal catalyst is palladium acetate or palladium chloride; the ligand is 2-dicyclohexyl phosphine-2 ',6' -dimethoxy biphenyl or triphenylphosphine; the alkali is potassium phosphate or triethylamine; the solvent S1Is tetrahydrofuran or toluene.
4. The method of synthesis according to claim 1, characterized in that: in the step (2), the oxidant is 2, 3-dichloro-5, 6-dicyano-1, 4-benzoquinone, manganese dioxide or benzoyl peroxide; the solvent S2Toluene, benzene, or carbon tetrachloride.
5. A method of making a substituted APD derivative from APD comprising the steps of:
(1) bromo-cyclohepta [ fg ] acenaphthylene (9) is prepared by bromination, the reaction formula and reaction process are as follows:
Figure FDA0002991060920000021
adding 1 equivalent of compound APD, 1-4 equivalents of bromine source and 0-4 equivalents of auxiliary agent into a reaction bottle, and adding the mixture into a solvent S3Medium heating to temperature T3Reacting for 4-24 hours to obtain the compound bromo cyclohepta [ fg]An acenaphthylene (9),
wherein the content of the first and second substances,
the bromine source is a compound capable of providing bromine atoms or bromine positive ions and comprises liquid bromine, N-bromosuccinimide, phenyltrimethyl ammonium tribromide or dibromohydantoin;
the auxiliary agent is a compound capable of promoting bromine free radicals or bromine positive ions to generate, and comprises benzoyl peroxide, ferric trichloride or acetic acid;
the solvent S3And corresponding temperature T3Comprises the following steps: dichloromethane, 25-40 ℃; 1, 2-dichloroethane, 25-80 ℃; tetrahydrofuran, 25-70 ℃; 1, 4-dioxane at 25-100 ℃); toluene, 25-120 ℃; benzene, 25-80 ℃; xylene, 25-130 ℃; 25-165 ℃ of mesitylene; 25-180 ℃ of chlorobenzene; n, N-dimethylformamide at 25-150 ℃; methanol, 25-70 ℃; ethanol, 25-80 ℃; dimethyl sulfoxide, 25-160 ℃;
said temperature T3Is higher than solvent S3Melting point lower than solvent S3The temperature of the boiling point;
the concentration C3As a reactant in a reaction solvent S3In the range of 0.1mM to 2M;
the product 9 is substituted by dibromine or monobromine;
(2) compound 10 was prepared by a transition metal coupling reaction, the reaction scheme and procedure were as follows:
Figure FDA0002991060920000031
adding 1 equivalent of the compound 9a prepared in the step (1), 0.01-0.2 equivalent of a transition metal catalyst and 2-4 equivalents of a fragment containing an R group into a reaction bottle, and dissolving the mixture in a solvent S4Medium heating to temperature T4Carrying out reaction for 4-24 hours to obtain a product 10,
wherein the transition metal catalyst is selected from palladium acetate, palladium tetratriphenylphosphine and palladium ditriphenylphosphine dichloride;
the R group-containing segment is selected from cuprous cyanide, zinc cyanide, carbon monoxide, a substituted or unsubstituted aryl or heteroaryl containing boronic acid, a tin reagent, a Grignard reagent, or a zinc reagent;
the additive is selected from triphenylphosphine, diadamantyl butyl phosphine, 2-dicyclohexylphosphine-2 ',6' -dimethoxy-biphenyl, alkylamine of C1-C10, sodium tert-butoxide, potassium tert-butoxide, 1, 8-diazabicycloundecen-7-ene or potassium phosphate;
the solvent S4And corresponding temperature T4Comprises the following steps: dichloromethane, 25-40 ℃; 1, 2-dichloroethane, 25-80 ℃; tetrahydrofuran, 25-70 ℃; 1, 4-dioxane, 25-100 ℃; toluene, 25-120 ℃; benzene, 25-80 ℃; xylene, 25-130 ℃; 25-165 ℃ of mesitylene; straight chain alkane of C5-C10, 25-boiling point; n, N-dimethylformamide at 25-140 ℃; 25-160 ℃ of N, N-dimethylacetamide;
the concentration C4As a reactant in a reaction solvent S4The concentration of (B) is in the range of 0.01M to 0.5M.
6. The method of claim 5, wherein: the R group in the step (2) is any one of the following groups:
Figure FDA0002991060920000032
the obtained product is any one of the following products:
Figure FDA0002991060920000041
7. the method according to claim 5 or 6, characterized in that: the transition metal catalyst is palladium acetate; the R group-containing segment is a boronic acid, tin reagent, grignard reagent, or zinc reagent containing a substituted or unsubstituted aryl or heteroaryl group; the additive is 2-dicyclohexylphosphine-2 ',6' -dimethoxy-biphenyl and potassium phosphate; the solvent is tetrahydrofuran.
8. A substituted APD derivative having the general formula:
Figure FDA0002991060920000042
wherein R is1、R2、R3、R4、R5、R6、R7、R8、R9And R10Is hydrogen, halogen or cyano, or is optionally substituted aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, alkyl, cycloalkyl, alkoxy, aryloxy, heteroaryloxy, arylthio, heteroarylthio or alkyl-substituted silicon, where R is1～R10Not hydrogen at the same time.
9. The substituted APD derivative of claim 8, wherein: the R is2～R9Are each hydrogen, said substituted APD derivative having any of the following structures:
Figure FDA0002991060920000051
10. a non-benzene polycyclic aromatic compound having APD as a core skeleton, having the following general formula (4):
Figure FDA0002991060920000052
wherein rings A, B, C, D, E, F, G, H, I, J are each independently hydrogen, an aromatic ring group or a heteroaromatic ring group, which rings cannot both be hydrogen,
X1、X2、X3、X4、X5、X6、X7、X8、X9and X10Each independently of the others, hydrogen, halogen or cyano, or an optionally substituted aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, alkyl, optionally substituted cycloalkyl, alkoxy, aryloxy, heteroaryloxy, arylthio, heteroarylthio or alkyl-substituted silicon group,
preferably, the non-benzene polycyclic aromatic compound has any one of the following structures:
Figure FDA0002991060920000061
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