CN112778347B - Synthetic method of boron nitrogen benzocarbazole derivative - Google Patents
Synthetic method of boron nitrogen benzocarbazole derivative Download PDFInfo
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Abstract
The invention relates to a synthesis method of a boron nitrogen benzocarbazole derivative, which comprises the steps of adding an o-aminostyrene derivative, an aryl fluoroborate derivative, ammonia gas or organic amine and a composite catalyst into a nitrogen atmosphere, heating to 25-100 ℃ to react for 1-24h, and extracting, drying and recrystallizing a product to obtain the boron nitrogen benzocarbazole derivative. According to per millimole of the aryl fluoborate derivative, the solvent amount is 5mL, the o-aminostyrene derivative amount is 1.2-1.5 mmol, the ammonia gas or organic amine amount is 0.35-6 mmol, the organic palladium and the phosphine compound amount are respectively 0.5-10 percent and 1-20 percent of the aryl fluoborate derivative mole percentage, and the alkaline compound amount is 1-6mmol. The invention has the advantages of mild reaction conditions, wide raw material application range, strong reaction specificity, high yield and little environmental pollution.
Description
Technical Field
The invention relates to a synthesis method of a boron nitrogen benzocarbazole derivative, and particularly belongs to the technical field of synthesis of boron nitrogen aromatic compounds.
Background
The organic conjugated material with photoelectric activity is one of the hot spots of research and development at present due to its wide application prospects in the fields of Organic Field Effect Transistors (OFETs), organic Light Emitting Diodes (OLEDs), organic solar cells (OPVs), organic sensors and the like. The design and synthesis of organic functional materials with novel structures have very important significance for improving the performance of organic electronic devices, and promote the development of organic electronics from the source. The organic functional material is mostly a small molecule or a polymer with a pi conjugated structure. By adjusting the molecular structure and the intermolecular interaction, the electronic structure and the spatial three-dimensional structure of the material can be regulated and controlled. Due to the special orbital interaction between main group elements such as boron, silicon, phosphorus and the like and a pi conjugated system and the characteristics of the self space structure, the introduction of the main group elements into the pi conjugated skeleton has important significance for adjusting the electronic structure and the solid structure of molecules. Therefore, in recent years, organic pi-conjugated materials containing main group elements have attracted much research interest, and especially, introduction of boron atoms into organic functional compounds has become leading and hot research contents in the field of organic photoelectric materials. For example, C = C double bonds in an organic pi conjugated system are replaced by B-N units, so that a boron-nitrogen aromatic system with a novel structure can be constructed. Researches prove that the boron-nitrogen aromatic system has excellent photoelectric properties, has better device performance, and has great potential and development space in the field of new materials.
However, the construction methods of boron-nitrogen aromatic compounds are not limited, and they can be roughly classified into three main groups:
(a) Olefin metathesis ring-closing reaction (Org. Let. 2000, 2, 2089；Org. Lett.2007, 94905; CN 104098597B), the method has longer reaction route, lower overall yield, can not prepare a large amount of target compounds, uses a plurality of toxic and sensitive reagents in the synthesis process, and has larger toxicity to the environment and human body.
(b) Lewis acid base chelation reaction (J. Am. Chem. Soc.2006, 128, 10885；Angew. Chem. Int. Ed. 2013,529966.) this method is relatively narrow in applicability, effective only for a particular structural type of compound, and not universal.
(c) Electrophilic boriding (CN 1130396109A;Dalton Trans. 2016, 45,5920；Angew. Chem. Int. Ed.,2012, 516074.) is the mainstream method for synthesizing aromatic compounds containing boron and nitrogen at present, the method has great limitation, boron atoms are introduced in the last step, sensitive boron-bromine compounds are used, and the problems of harsh reaction conditions, unstable raw materials, difficult synthesis of precursors, complex reaction process, complicated post-treatment, poor substrate compatibility, difficult functionalization of products and the like exist, so that the synthesis of boron-nitrogen frameworks with novel structures is difficult to realize, and particularly the construction of some star molecule analogues. This situation hinders the organoboron chemistry and the organoboron compound in functional materials and the like to some extentFurther applications in the field. Therefore, a new synthesis strategy is established, and the accurate construction of the boron-nitrogen aromatic compound with various forms, novel structure and excellent comprehensive performance is a problem to be solved in the field.
In conclusion, the invention breaks through the traditional thought, combines the modern synthesis methodology, provides a new method for constructing the boron-nitrogen aromatic compound, selects commercial cheap and easily-obtained organic compounds as starting materials, enlarges a boron-nitrogen conjugated system through high-efficiency transition metal catalytic series reaction, finally realizes the precise construction of a brand new boron-nitrogen aromatic compound, solves the problem of difficult boronization reaction, develops the variety and construction method of the boron-nitrogen fused ring compound, and has important significance for the research and application of the materials.
Disclosure of Invention
Aiming at the current situation, the invention provides a synthesis method of a boron nitrogen benzocarbazole derivative.
The invention relates to a synthetic method of a boron-nitrogen benzocarbazole derivative, which comprises the following steps: adding an o-aminostyrene derivative, an aryl fluoroborate derivative, ammonia gas or organic amine and a composite catalyst into a reaction container, vacuumizing and exchanging nitrogen, adding a solvent, heating to 25-100 ℃ to react for 1-24h, and extracting, drying and recrystallizing a product to obtain a boron-nitrogen benzocarbazole derivative; the composite catalyst is a composition of organic palladium, a phosphine compound and an alkaline compound;
wherein: based on each millimole of the aryl fluoroborate derivative, the dosage of the solvent is 5mL, the dosage of the o-aminostyrene derivative is 1.2-1.5 mmol, the dosage of the ammonia gas or the organic amine is 0.35-6 mmol, the dosage of the organic palladium is 0.5-10% of the mole percent of the aryl fluoroborate derivative, the dosage of the phosphine compound is 1-20% of the mole percent of the aryl fluoroborate derivative, and the dosage of the alkaline compound is 1-6mmol.
The o-aminostyrene derivative is fluorine atom or methyl substituted o-aminostyrene.
The aryl fluoroborate derivative is phenyl or thiophene group substituted fluoroborate.
The organic amine is aniline, p-methoxyaniline or p-trifluoromethylaniline.
The organic palladium is palladium acetate, bis (triphenylphosphine) palladium dichloride, [1, 1-bis (diphenylphosphino) ferrocene ] palladium dichloride, bis (dibenzylideneacetone) palladium or allyl palladium (II) chloride dimer.
The phosphine compound is triphenylphosphine, 2- (di-tert-butylphosphine) biphenyl, 2-dicyclohexylphosphine-2 ',6' -dimethoxy-1, 1 '-biphenyl, tricyclohexylphosphine or 2-dicyclohexylphosphine-2', 4',6' -triisopropylbiphenyl.
The alkaline compound is sodium carbonate, sodium bicarbonate, sodium acetate, sodium tert-butoxide, potassium acetate, potassium tert-butoxide or potassium carbonate.
The solvent is dimethylformamide, toluene or tetrahydrofuran.
The general formula of the reaction of the present invention is:
the invention has the beneficial effects that:
(1) The method realizes the precise synthesis of a novel boron-nitrogen fused ring compound by three components of high-efficiency series reaction of 'one-pot' and has important guiding significance for the design and synthesis of boron-nitrogen aromatic compounds, and the method has the advantages of wide raw material application, simple reaction, strong reaction specificity and high yield;
(2) The raw materials of the invention are cheap and easy to obtain, for example, aniline is a very cheap chemical raw material; the involved reactions do not involve air-sensitive toxic substances, and the method is very environment-friendly; the reaction steps are simple, the side reaction is less, the post-treatment is simple and efficient, and only the most basic operations such as extraction, recrystallization and the like are needed; the reaction condition is mild and easy to realize, harsh reaction conditions such as high temperature, high pressure and the like are not involved, and the reaction temperature is generally controlled between room temperature and 100 ℃;
(3) The compounds related by the invention are synthesized for the first time, and are not reported in the literature, and the compounds cannot be synthesized by the existing method for synthesizing the borazine aromatic compound;
(4) The boron azacarbazole and the derivatives thereof covered by the invention are important intermediates in various fields such as biomedicine, photoelectric materials and the like, and have important significance for the development of modern synthesis methodology, biological materials and material science.
1 HNMR data, 13 C、 11 B NMR data were obtained using a 400M superconducting NMR spectrometer from Bruker, using deuterated chloroform as solvent, TMS, BF 3 The ether solution was used as a reference for the measurement.
Detailed Description
The following is a preferred embodiment of the present invention, and it should be noted that it is obvious to those skilled in the art that various modifications and improvements can be made without departing from the principle of the present invention, and these modifications and improvements are also considered to be within the scope of the present invention.
Example 1
Synthesis of the compound:
A2L dry three-necked flask was evacuated and purged with argon 3 times, and under nitrogen protection, o-aminostyrene (14.4 g, 0.12 mol), potassium phenylo-bromofluoroborate (26.2 g, 0.1 mol), silicon tetrachloride (17.0 g, 0.1 mol), aniline (9.5 g, 0.12 mol), bis (dibenzylideneacetone) palladium (575 mg,1 mol), 2-dicyclohexylphosphine-2 ',4',6' -triisopropylbiphenyl (952 mg,2 mol%), sodium tert-butoxide (11.5 g, 0.12 mol) were sequentially added, and toluene (500 mL) as an anhydrous oxygen-free solvent was introduced. And (3) reacting at 100 ℃ for about 8 hours under the protection of argon, finishing the reaction, cooling the temperature of the system to room temperature, extracting with ethyl acetate (4X 1L) and water (2L), drying, and recrystallizing to obtain 25.6 g of white solid with the yield of 87%.
The nmr data for this compound are as follows:
1 H NMR (400 MHz, CDCl 3 ): δ 8.63 (1H, s, NH), 8.42 (1H, s), 8.23 (1H, d, J = 12 Hz), 7.82 (2H, t, J = 8 Hz), 7.48-7.69 (3H, m), 7.22-7.36 (7H, m). 13 C NMR (101 MHz, CDCl 3 ) Delta 158.3, 137.6,136.2, 134.3, 133.5, 132.6, 131.7, 130.5, 128.7, 127.3, 126.4, 125.7, 123.7, 123.5, 121.6, 118.9. The carbon attached to the boron atom has no signal response.
Example 2
Synthesis of the compound:
A2L dry three-necked flask was taken, vacuum-evacuated and argon-exchanged for 3 times, and under nitrogen protection, o-aminostyrene (14.4 g, 0.12 mol), potassium phenylo-bromofluoroborate (26.2 g, 0.1 mol), silicon tetrachloride (17.0 g, 0.1 mol), p-anisidine (14.8 g, 0.12 mol), bis (dibenzylideneacetone) palladium (290 mg, 0.5 mol%), 2-dicyclohexylphosphino-2 ',4',6' -triisopropylbiphenyl (480 mg,1 mol%), sodium tert-butoxide (11.5 g, 0.12 mol) were added in this order, and toluene (500 mL) as an anhydrous oxygen-free solvent was introduced. And (3) reacting at 80 ℃ for about 4 hours under the protection of argon, finishing the reaction, cooling the temperature of the system to room temperature, extracting with ethyl acetate (4X 1L) and water (2L), combining organic phases, drying with anhydrous sodium sulfate, and recrystallizing to obtain a white solid with the yield of 26.9g and 83%.
The nmr data for this compound are as follows:
1 H NMR (400 MHz, CDCl 3 ): δ 8.56 (1H, s, NH), 8.31 (1H, s), 8.16 (1H, m), 7.73 (2H,m), 7.36-7.56(3H, m), 7.12-7.24 (6H, m),3.67(3H, OCH 3 ). 13 C NMR (101 MHz, CDCl 3 ) Delta 156.7, 149.7, 135.8,134.6, 133.8, 131.6, 130.4, 128.7, 127.6, 125.9, 124.7, 123,8, 122.6, 121.8, 120.9, 116.8. The carbon attached to the boron atom has no signal response.
Example 3
Synthesis of the compound:
A2L dry three-necked flask was taken, evacuated and argon-exchanged 3 times, and under nitrogen protection, o-aminostyrene (14.4 g, 0.12 mol), potassium phenyl o-bromofluoroborate (26.2 g, 0.1 mol), silicon tetrachloride (17.0 g, 0.1 mol), p-trifluoromethylaniline (19.4 g, 0.12 mol), allylpalladium (II) chloride dimer (183 mg, 0.5 mol%), 2- (di-t-butylphosphine) biphenyl (298 mg, 1mol%), sodium t-butoxide (11.5 g, 0.12 mol) were added in this order, and tetrahydrofuran (500 mL) as an anhydrous oxygen-free solvent was introduced. Reacting at 60 ℃ for about 8 hours under the protection of argon, finishing the reaction, cooling the temperature of the system to room temperature, extracting with ethyl acetate (4X 1L) and water (2L), combining organic phases, drying with anhydrous sodium sulfate, and recrystallizing to obtain a white solid with the yield of 28.2g and 78%.
The nmr data for this compound are as follows:
1 H NMR (400 MHz, CDCl 3 ): δ 8.89 (1H, s, NH), 8.51 (1H, s), 8.32 (1H, m), 7.96 (2H,m), 7.62-7.83 (3H, m), 7.32-7.54 (6H, m). 13 C NMR (101 MHz, CDCl 3 ): δ 146.7, 145.3,144.3, 139.4,134.6,137.3, 136.2, 133.5, 132.4, 131.2, 130.6, , 128,7, 126.9, 125.4, 124.7(J C-F = 272.7 Hz, CF 3 ),121.9, 118.2. The carbon attached to the boron atom has no signal response.
Example 4
Synthesis of the compound:
A2L dry three-necked flask was taken, vacuum-evacuated and argon-exchanged for 3 times, and under nitrogen protection, 4-methyl o-aminostyrene (16.0 g, 0.12 mol), potassium phenyl o-bromofluoroborate (26.2 g, 0.1 mol), silicon tetrachloride (17.0g, 0.1 mol), aniline (9.5 g, 0.12 mol), bis (triphenylphosphine) palladium dichloride (702 mg,1 mol%), triphenylphosphine (524 mg,2 mol%), sodium carbonate (12.8 g, 0.12 mol) were added in this order, and anhydrous oxygen-free solvent DMF (500 mL) was introduced. And (3) reacting at 100 ℃ for about 12 hours under the protection of argon, finishing the reaction, cooling the temperature of the system to room temperature, extracting with ethyl acetate (4X 1L) and water (2L), combining organic phases, drying with anhydrous sodium sulfate, and recrystallizing to obtain 27.8g of white solid with the yield of 88%.
The nmr data for this compound are as follows:
1 H NMR (400 MHz, CDCl 3 ): δ 8.59 (1H, s, NH), 8.39 (1H, s), 8.13 (1H, d, J = 12 Hz), 7.72 (2H, M), 7.36-7.49 (2H, m), 7.18-7.29 (7H, m),2.36 (s, CH 3 ). 13 C NMR (101 MHz, CDCl 3 ) Delta 156.3, 146.8, 135.3, 133.1, 132.4, 132.7, 131.6, 130.5, 128.9, 126.6, 125.9, 124.7, 122.9, 121.8, 120.6, 119.9, 21.3. The carbon attached to the boron atom has no signal response.
Example 5
Synthesis of the compounds:
A2L dry three-necked flask was taken, vacuum-pumped and argon-exchanged for 3 times, and 3-fluoro-o-aminostyrene (16.4 g, 0.12 mol), potassium phenyl o-bromofluoroborate (26.2 g, 0.1 mol), silicon tetrachloride (17.0g, 0.1 mol), aniline (9.5 g, 0.12 mol), palladium acetate (224 mg,1 mol%), tricyclohexylphosphine (560 mg,2 mol%), sodium acetate (16.3 g, 0.12 mol) were added in this order under nitrogen protection, and anhydrous oxygen-free solvent DMF (500 mL) was introduced. And (3) reacting at 90 ℃ for about 12 hours under the protection of argon, finishing the reaction, cooling the temperature of the system to room temperature, extracting with ethyl acetate (4X 1L) and water (2L), combining organic phases, drying with anhydrous sodium sulfate, and recrystallizing to obtain 23.7g of white solid with the yield of 76%.
The nmr data for this compound are as follows:
1 H NMR (400 MHz, CDCl 3 ): δ 8.89 (1H, s, NH), 8.33 (1H, s), 8.20(1H, d, J = 12 Hz), 7.86 (2H, m), 7.48-7.69 (2H, m), 7.28-7.39 (7H, m). 13 C NMR (101 MHz, CDCl 3 ): δ 160.2(d, J C-F = 252.5 Hz), 144.5 , 142.7 (d, J C-F = 5.1 Hz), 141.4, 100.5, 138.3, 134.1 (d, J C-F = 7.1 Hz), 133.6, 130.8, 129.4, 129.3, 128.8 (d, J C-F = 10.1 Hz), 125.4, 116.3 (d, J C-F = 16.2 Hz), 112.6 (d, J C-F = 3.0 Hz,), 106.2 (d, J C-F = 21.2 Hz). The carbon attached to the boron atom has no signal response.
Example 6
Synthesis of the compounds:
A2L dry three-necked flask was taken, vacuum-evacuated and argon-exchanged for 3 times, and under nitrogen protection, o-aminostyrene (14.4 g, 0.12 mol), potassium 4-fluoro-phenyl o-bromofluoroborate (28.0 g, 0.1 mol), silicon tetrachloride (17.0g, 0.1 mol), aniline (9.5 g, 0.12 mol), bis (dibenzylideneacetone) palladium (575 mg,1 mol%), 2-dicyclohexylphosphine-2 ',4',6' -triisopropylbiphenyl (952 mg,2 mol%), sodium tert-butoxide (11.5 g, 0.12 mol) were added in this order, and toluene (500 mL) as an anhydrous oxygen-free solvent was introduced. And (3) reacting at 100 ℃ for about 10 hours under the protection of argon, finishing the reaction, cooling the temperature of the system to room temperature, extracting with ethyl acetate (4X 1L) and water (2L), combining organic phases, drying with anhydrous sodium sulfate, and recrystallizing to obtain a white solid 24.9g with the yield of 80%.
The nmr data for this compound are as follows:
1 H NMR (400 MHz, CDCl 3 ): δ 8.91 (1H, s, NH), 8.37 (1H, s), 8.18 (1H, d, J = 12 Hz), 7.76 (2H, m), 7.38-7.63 (2H, m), 7.08-7.28 (7H, m). 13 C NMR (101 MHz, CDCl 3 ): δ164.3 (d, J C-F = 248.5 Hz), 145.7 (d, J C-F = 8.1 Hz), 143.0, 141.6, 100.7, 139.9, 131.0, 130.7, 129.1, 127.8, 126.1, 125.4, 121.1, 118.4, 115.0(d, J C-F = 21.2 Hz), 112.8(d, J C-F = 22.2 Hz). The carbon attached to the boron atom has no signal response.
Example 7
Synthesis of the compound:
A2L dry three-necked flask was taken, vacuum-evacuated and argon-exchanged for 3 times, and N-N-butyl-o-aminostyrene (21.0 g, 0.12 mol), potassium phenylo-bromofluoroborate (26.2 g, 0.1 mol), silicon tetrachloride (17.0g, 0.1 mol), aniline (9.5 g, 0.12 mol), bis (dibenzylideneacetone) palladium (575 mg,1 mol%), 2-dicyclohexylphosphine-2 ',4',6' -triisopropylbiphenyl (952 mg,2 mol%), sodium tert-butoxide (11.5 g, 0.12 mol) were added in this order under nitrogen protection, and toluene (500 mL) as an anhydrous oxygen-free solvent was introduced. And (3) reacting at 70 ℃ for about 7 hours under the protection of argon, finishing the reaction, cooling the temperature of the system to room temperature, extracting with ethyl acetate (4X 1L) and water (2L), combining organic phases, drying with anhydrous sodium sulfate, and recrystallizing to obtain 25.6 g of white solid with the yield of 87%.
The nmr data for this compound are as follows:
1 H NMR (400 MHz, CDCl 3 ): δ 8.03 (1H, d, J = 8 Hz), 7.95 (1H, s), 7.88 (1H, d, J = 8 Hz), 7.64-7.71 (2H, m), 7.47-7.55 (2H, m), 7.39-7.41 (1H, m), 7.13-7.24 (5H, m,), 4.56-5.15 (2H, m), 2.24-2.39 (2H, m), 1.76-1.77 (2H, m), 1.12 (3H, t, J = 6 Hz). 13 C NMR (101 MHz, CDCl 3 ) Delta 144.5, 142.6, 141.7, 100.6, 138.2, 133.4, 131.5, 129.5, 129.2, 127.6, 126.2, 126.0, 125.9, 125.1, 120.6, 115.4, 49.2, 32.1, 20.3, 14.1. The carbon attached to the boron atom has no signal response.
The above examples only express the specific embodiments of the present invention, and the description thereof is more specific and detailed, but not to be construed as limiting the scope of the present invention. It should be noted that various changes and modifications can be made by those skilled in the art without departing from the spirit of the invention, and these changes and modifications are all within the scope of the invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (2)
1. A synthetic method of boron nitrogen benzocarbazole derivative is characterized by comprising the following steps: the synthesis method comprises the following steps: adding an o-aminostyrene derivative, an aryl fluoroborate derivative, organic amine and a composite catalyst into a reaction container, vacuumizing to exchange nitrogen, adding a solvent, heating to 60-100 ℃ to react for 4-12 hours, and extracting, drying and recrystallizing a product to obtain a boron-nitrogen benzocarbazole derivative; the composite catalyst is a composition of organic palladium, a phosphine compound, an alkaline compound and silicon tetrachloride;
wherein: based on per millimole of the aryl fluoroborate derivative, the dosage of the solvent is 5mL, the dosage of the o-aminostyrene derivative is 1.2-1.5 mmol, the dosage of the organic amine is 0.35-6 mmol, the dosage of the organic palladium is 0.5-10% of the mole percent of the aryl fluoroborate derivative, the dosage of the phosphine compound is 1-20% of the mole percent of the aryl fluoroborate derivative, the dosage of the alkaline compound is 1-6mmol, and the dosage of the silicon tetrachloride is 1mmol;
the organic palladium is palladium acetate, bis (triphenylphosphine) palladium dichloride, bis (dibenzylideneacetone) palladium or allyl palladium chloride (II) dimer;
the phosphine compound is triphenylphosphine, 2- (di-tert-butylphosphine) biphenyl, tricyclohexylphosphine or 2-dicyclohexylphosphine-2 ',4',6' -triisopropylbiphenyl;
the alkaline compound is sodium carbonate, sodium acetate and sodium tert-butoxide;
the reaction general formula for synthesizing the boron nitrogen benzocarbazole derivative is as follows:
wherein: r is 1 = H、CH 3 Or F; r 2 = H or n-butyl; r 3 = Br；R 4 = H、CH 3 Or F; r 5 = phenyl, M = potassium.
2. The method for synthesizing a boratabenzocarbazole derivative according to claim 1, wherein: the solvent is dimethylformamide, toluene or tetrahydrofuran.
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