CN114716454A - Nitrogen and oxa condensed ring aromatic hydrocarbon and synthetic method thereof - Google Patents

Abstract

The invention provides nitrogen and oxa condensed ring aromatic hydrocarbons and a synthesis method thereof, which are used for solving the technical problems of single synthesis method of the existing condensed ring aromatic hydrocarbons, complex substrate synthesis, limited product structure and the like. The synthesis method comprises the following steps: adding the oxazine compound 1, the diazo compound 2, the catalyst and the additive into a solvent in an inert atmosphere, reacting in the inert atmosphere, and obtaining the hetero-condensed ring aromatic compound 3 after the reaction is finished. The invention provides a simple and effective synthesis method for the synthesis of polycyclic aromatic hydrocarbon containing multiple heteroatoms, and the method has the characteristics of mild reaction conditions, simple operation, atom economy, economic steps, strong functional group tolerance, good yield and the like. The obtained product has wide industrial application prospect, and provides a new idea and a new method for the fields of medicine, natural product synthesis, luminescent materials and the like.

Description

A kind of nitrogen, oxygen heterocyclic aromatic hydrocarbon and its synthesis method

technical field

The invention belongs to the technical field of organic synthetic chemistry, and in particular relates to a nitrogen, oxygen heterocyclic aromatic hydrocarbon and a synthesis method thereof.

Background technique

Polycyclic aromatic hydrocarbons refer to polycyclic aromatic hydrocarbon compounds composed of two or more aromatic hydrocarbons, which are widely used in pharmaceuticals, dyes and other industries. There are π-π interactions in the crystal arrangement of fused ring aromatic hydrocarbons, and an ordered stacking is formed between the molecules, which is used in organic optoelectronic devices (including organic field-effect transistors (Organic Field-Effect Transistor, OFET), organic solar cells (Organic Solar Cell, OSC) and organic light-emitting diodes (Organic Light-Emitting Diode, OLED, etc.), organic semiconductor materials and other fields have broad application prospects (Chem. Rev., 2007, 107, 926; Chem. Soc. Rev., 2010, 39, 1489; Chem. Soc. Rev., 2012, 41, 4245; Nature, 2004, 428, 911). Compared with traditional inorganic optoelectronic materials, large-sized conjugated molecules have the advantages of molecular-level structure adjustment; good solubility and easy processing; light weight and flexibility, which can realize the preparation of large-area devices. Therefore, designing and synthesizing new organic fused-ring aromatic hydrocarbons, and conducting research on their properties and applications has always been one of the research hotspots of scientists in the fields of chemistry, materials and biology. In particular, replacing some carbon atoms in polycyclic compounds with heteroatoms to form heteroatom-containing conjugated skeleton molecules, namely hetero-fused aromatic hydrocarbons, can significantly improve the stability and assembly performance of the materials, thereby significantly improving the optoelectronic properties of organic optoelectronic materials. Performance and versatility (Angew. Chem., Int. Ed., 2010, 49, 8209; Chem. Mater., 2015, 28, 3). At the same time, multifunctional modification of fused-ring aromatic hydrocarbons is also an important means to endow organic optoelectronic molecules with controllability and diversity.

Due to the advantages of high atomic economy and step economy, the direct functionalization of inert C-H bonds has become an undisputed ideal synthetic method pursued by chemists, and it was once called "the holy grail of chemistry". In the past 20 years, transition metal-catalyzed C-H activation reactions have indeed achieved remarkable results, realizing many transformations that cannot be accomplished by traditional chemistry. Among them, the synthesis of rhodium-catalyzed C-H bond activated 1:2 coupling to construct polycyclic aromatic hydrocarbons has been rapidly developed, and a large number of novel fused-ring aromatic hydrocarbon frameworks with important application prospects in the field of organic optoelectronic materials and pharmaceuticals have been prepared. However, as important intermediates in organic synthesis, the application of diazonium compounds in transition metal-catalyzed 1:2 coupling to construct fused heterocyclic aromatic hydrocarbons is still in its infancy. So far, there is only one report on rhodium-catalyzed C-H-directed C-H activation for 1:2 coupling to construct condensed aromatic hydrocarbon molecules (Org. Lett. 2017, 19, 2294), and the research is relatively slow. In the above method, the strongly coordinated pyridine compound is used as the guiding group, and the 1:2 coupling with the diazo compound is realized under the action of rhodium catalyst, and a series of naphthoquinolinone skeletons are constructed.

On the one hand, the directing group used in the existing synthesis methods is pyridine with strong coordination ability, the substrate synthesis is complex, the product type is single, and the obtained skeleton is only a condensed aromatic hydrocarbon with aza. On the other hand, benzoxazine imines, as key intermediates in organic synthesis, have simple synthesis and wide sources. The use of it as a weak directing group in the rhodium-catalyzed 1:2 coupling of carbene has not been reported. According to existing literature reports, hetero-fused aromatic hydrocarbons can significantly improve the stability and assembly performance of materials, thereby significantly improving the optoelectronic properties and multifunctionality of organic optoelectronic materials (Angew.Chem., Int.Ed., 2010,49, 8209; Chem.Mater., 2015, 28, 3), the application of hetero-fused aromatic hydrocarbons in organic optoelectronic materials has broad prospects; therefore, it is urgent to find a new method for the synthesis of hetero-fused aromatic hydrocarbons.

SUMMARY OF THE INVENTION

In view of the technical problems such as single synthesis method of existing fused heterocyclic aromatic hydrocarbons, complex synthesis of substrates and limited product structure, the present invention provides a nitrogen, oxygen heterocyclic aromatic hydrocarbon and a synthesis method thereof. The present invention is a fused ring aromatic hydrocarbon containing multiple heteroatoms The synthesis provides a simple and effective synthetic method, and the method has the characteristics of mild reaction conditions, simple operation, atom economy, step economy, strong functional group tolerance and good yield.

In order to achieve the above object, the technical scheme of the present invention is achieved in this way:

A nitrogen, oxygen heterocyclic aromatic hydrocarbon, the structural formula is as follows:

Wherein R is any one of H, Me, OMe, F, Cl or Br; R ¹ is any one of Me, n-Pr or Ph; R ² is n-Am or ⁱ Pr; Ar is Me, OMe, A benzene ring substituted by any one of F, Cl, Br, Ph or CF ₃ .

The synthetic method of above-mentioned nitrogen and oxygen heterocyclic aromatic hydrocarbons comprises the following steps: adding an oxazine compound 1, a diazo compound 2, a catalyst and an additive into a solvent and reacting under an inert atmosphere, and obtaining the heterofused ring aromatic hydrocarbons after the reaction finishes Compound 3, the reaction equation is:

Wherein R is any one of H, Me, OMe, F, Cl or Br; R ¹ is any one of Me, n-Pr or Ph; R ² is n-Am or ⁱ Pr; Ar is Me, OMe, A benzene ring substituted by any one of F, Cl, Br, Ph or CF ₃ ; where Rh(III) is a catalyst.

After the reaction is completed, the solution after the reaction is separated and purified to obtain the hetero-fused ring aromatic hydrocarbon compound 3.

During the reaction, the reaction temperature is 80-120° C., and the reaction time is 6-12 h.

The catalyst comprises a rhodium catalyst and a silver salt; the molar ratio of the rhodium catalyst and the silver salt is 1:4; the rhodium catalyst is a dichloro(pentamethylcyclopentadienyl) rhodium dimer, a pentamethyl ring Pentadienyl rhodium acetate or bis(hexafluoroantimonate) triacetonitrile (pentamethylcyclopentadienyl) rhodium any one or combination; silver salt is silver hexafluoroantimonate, silver tetrafluoroborate, bistri Any one or combination of silver fluoromethanesulfonimide, silver trifluoromethanesulfonate, silver sulfate, silver acetate, and silver trifluoroacetate.

The catalyst is composed of dichloro(pentamethylcyclopentadienyl) rhodium dimer and silver hexafluoroantimonate; dichloro(pentamethylcyclopentadienyl) rhodium dimer and hexafluoroantimony The molar ratio of silver acid is 1:4.

The additive is any one or a combination of 2,4,6-trimethylbenzoic acid, pivalic acid, acetic acid, 1-adamantanecarboxylic acid, zinc acetate, sodium carbonate, potassium acetate or potassium carbonate.

The solvent is any one or a combination of dichloroethane (DCE), methanol (MeOH), acetonitrile (MeCN), 1,4-dioxane (1,4-dioxane) or toluene (toluene).

The inert atmosphere is a nitrogen atmosphere, and can also be a gas atmosphere such as helium, neon, and argon.

The molar ratio of the oxazine compound 1, the diazo compound 2, the catalyst, the additive and the solvent is: 1:(2-3):(0.02-0.04):(0.08-0.16).

The concentration of the reaction system in the solvent is 0.05M-0.2M.

For the reaction mode of this reaction, the reaction principle is shown in Figure 31: First, the substrate 1a and the catalyst act to obtain the cyclic metal intermediate A, then the nitrogen-filled compound and the intermediate A react to obtain the intermediate B, and then the intermediate B occurs. The migration and insertion of carbene obtains intermediate C, then the removal of metal occurs to obtain intermediate D, and the above process occurs again for intermediate D to obtain double-alkylated intermediate E, intermediate E rapidly changes into enol form F, intermediate The hydroxyl group in F attacks the imine bond to obtain intermediate G, the NH of intermediate G performs nucleophilic addition-elimination to the carbonyl group of another molecule to obtain intermediate I, and then intermediate I undergoes acidification-ring-opening-ring-closing -Continuous transformations such as dehydration give the target nitrogen, oxygen heterocyclic aromatic hydrocarbons 3aa.

Beneficial effects of the present invention: the present invention creatively selects easily available oxazine compounds and diazonium compounds as reactants, and under the action of metal rhodium catalyst, takes the imine among the oxazine compounds as the weak reactive type Positioning base, the construction of a novel nitrogen and oxygen heterocyclic aromatic hydrocarbon skeleton is realized in one step through a continuous [4+2] tandem strategy. This method is simple to operate, has significant atom economy and step economy, and provides a good solution for the synthesis of heterocyclic aromatic hydrocarbons. A simple and effective method has been developed, and the reaction conditions of this method are mild, and the reaction temperature is only 80-120 ° C; in addition, the yield of the prepared nitrogen and oxygen heterocyclic aromatic hydrocarbons is good, and the yield is generally above 80%, the highest to 98%. The obtained product has broad industrial application prospects, and provides a new idea and a new method for the fields of medicine, natural product synthesis and luminescent materials.

Description of drawings

In order to illustrate the embodiments of the present invention or the technical solutions in the prior art more clearly, the following briefly introduces the accompanying drawings that are used in the description of the embodiments or the prior art. Obviously, the drawings in the following description are only These are some embodiments of the present invention. For those of ordinary skill in the art, other drawings can also be obtained according to these drawings without creative efforts.

Fig. 1 is the nuclear magnetic ¹ H spectrum of compound 3aa; Fig. 2 is the nuclear magnetic ¹³ C spectrum of compound 3aa.

Figure 3 is the NMR ¹ H spectrum of the compound 3ba; Figure 4 is the NMR ¹³ C spectrum of the compound 3ba.

FIG. 5 is the NMR ¹ H spectrum of the compound 3ca; FIG. 6 is the NMR ¹³ C spectrum of the compound 3ca.

FIG. 7 is the nuclear magnetic ¹ H spectrum of compound 3da; FIG. 8 is the nuclear magnetic ¹³ C spectrum of compound 3da.

Fig. 9 is the NMR ¹ H spectrum of the compound 3ea; Fig. 10 is the NMR ¹³ C spectrum of the compound 3ea.

Fig. 11 is the ^1H NMR spectrum of compound 3fa; Fig. 12 is the NMR ^13C spectrum of compound 3fa.

Figure 13 is the NMR ¹ H spectrum of the compound 3ga; Figure 14 is the NMR ¹³ C spectrum of the compound 3ga.

Figure 15 is the nuclear magnetic ¹ H spectrum of compound 3ha; Figure 16 is the nuclear magnetic ¹³ C spectrum of compound 3ha.

FIG. 17 is the ^1H NMR spectrum of compound 3ia; FIG. 18 is the ^13C NMR spectrum of compound 3ia.

Fig. 19 is the nuclear magnetic ¹ H spectrum of compound 3ja; Fig. 20 is the nuclear magnetic ¹³ C spectrum of compound 3ja.

Figure 21 is the nuclear magnetic ¹ H spectrum of compound 3ka; Figure 22 is the nuclear magnetic ¹³ C spectrum of compound 3ka.

Figure 23 is the nuclear magnetic ¹ H spectrum of compound 3ab; Figure 24 is the nuclear magnetic ¹³ C spectrum of compound 3ab.

Fig. 25 is the NMR ¹ H spectrum of compound 3ac; Fig. 26 is the NMR ¹³ C spectrum of compound 3ac.

Figure 27 is the nuclear magnetic ¹ H spectrum of compound 3ad; Figure 28 is the nuclear magnetic ¹³ C spectrum of compound 3ad.

Figure 29 is the nuclear magnetic ¹ H spectrum of compound 3ae; Figure 30 is the nuclear magnetic ¹³ C spectrum of compound 3ae.

Figure 31 is a diagram of the reaction mechanism of the present invention.

Detailed ways

The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the protection scope of the present invention.

Example 1

Under nitrogen, 3-arylbenzoxazine compound 1a (0.20 mmol), diazo compound 2a (0.44 mmol), [Cp*RhCl ₂ ] ₂ (4 mol %), AgSbF ₆ (16 mol %), MesCOOH (0.4 mmol) and solvent DCE (2.0 mL) were added into a 10 mL sealed tube, and reacted in a reaction module at 80 degrees for 10 h. After the reaction, the solvent was removed under reduced pressure, and the target product 5,12-dimethyl was obtained by separation with a silica gel column. Diethyl isoquinoline[2,1,8-mna]phenoxazine-4,13-dicarboxylate (3aa), all eluents were petroleum ether ethyl acetate and dichloromethane 30:1:1 proportions are prepared. Product data characterization: tan liquid, 78% yield. The NMR spectra of the products are shown in Figures 1 and 2, ¹ H NMR (400MHz, CDCl ₃ )δ7.23(d, J=8.6Hz, 1H), 7.11(t, J=8.0Hz, 1H), 7.03-6.97 (m, 1H), 6.94 (t, J=7.6Hz, 1H), 6.89 (d, J=7.7Hz, 1H), 6.82 (d, J=7.9Hz, 1H), 6.77 (d, J=7.3Hz) ,1H),4.49–4.38(m,4H),2.33(s,6H),1.45–1.40(m,6H). ¹³ CNMR(101MHz, CDCl ₃ )δ168.6,167.7,150.6,138.6,137.1,131.2,130.2 ,129.1,128.4,127.7,125.8,125.7,125.0,123.9,123.6,120.1,119.6,117.1,116.8,115.2,61.1,61.0,19.0,14.4,14.3,13.2.HRMS: [M+H] ⁺ calculated for C _{26 H24NO5} ⁺ : _430.1649 , found: 430.1635.

Example 2

Under nitrogen, 3-arylbenzoxazine compound 1b (0.20 mmol), diazo compound 2a (0.44 mmol), [Cp*RhCl ₂ ] ₂ (4 mol %), AgSbF ₆ (16 mol %), MesCOOH (0.4mmol) and solvent DCE (2.0mL) were added to a 10mL sealed tube, and reacted in a reaction module at 80 degrees for 10h. After the reaction, the solvent was removed under reduced pressure, and the target product 7-bromo-5,12 was obtained by separation with a silica gel column. - Diethylisoquinoline[2,1,8-mna]phenoxazine-4,13-dicarboxylate (3ba), all eluents were petroleum ether, ethyl acetate and dichloromethane as per 30 : 1:1 ratio is formulated. Characterization of product data: tan solid, 98% yield, melting range: 119-120°C. The nuclear magnetic spectrum of the product is shown in Figures 3 and 4, ¹ H NMR (400MHz, CDCl ₃ )δ7.26(t, J=8.3Hz, 2H), 7.14(t, J=8.0Hz, 1H), 6.86(t , J=8.0Hz, 1H), 6.79 (dd, J=7.5, 4.6Hz, 2H), 4.49–4.39 (m, 4H), 2.44 (s, 3H), 2.33 (s, 3H), 1.45–1.40 ( m, 6H). ¹³ C NMR (101MHz, CDCl ₃ )δ168.6, 167.6, 147.7, 138.0, 137.1, 132.0, 131.0, 129.2, 128.8, 128.7, 128.0, 126.3, 124.7, 124.6, 124.0, 120., 6, 118.5, 115.7, 111.2, 61.3, 61.2, 19.0, 14.4, 14.4, 13.5. HRMS: [M+H] ⁺ calculated for C ₂₆ H ₂₃ BrNO ₅ ⁺ : 508.0754, found: 508.0717.

Example 3

Under nitrogen, 3-arylbenzoxazine compound 1c (0.20 mmol), diazo compound 2a (0.44 mmol), [Cp*RhCl ₂ ] ₂ (4 mol %), AgSbF ₆ (16 mol %), MesCOOH (0.4mmol) and solvent DCE (2.0mL) were added to a 10mL sealed tube, and reacted in a reaction module at 80 degrees for 10h. After the reaction was completed, the solvent was removed under reduced pressure, and the target product 8-fluoro-5,12 was obtained by separation with a silica gel column. - Diethylisoquinoline[2,1,8-mna]phenoxazine-4,13-dicarboxylate (3ca), all eluents were petroleum ether, ethyl acetate and dichloromethane as per 30 : 1:1 ratio is formulated. Product Data Characterization: Yellow solid, 89% yield, melting range: 104-105°C. The nuclear magnetic spectrum of the product is shown in Figures 5 and 6, ¹ H NMR (400MHz, CDCl ₃ )δ7.26(t, J=8.3Hz, 2H), 7.14(t, J=8.0Hz, 1H), 6.86(t , J=8.0Hz, 1H), 6.79 (dd, J=7.5, 4.6Hz, 2H), 4.49–4.39 (m, 4H), 2.44 (s, 3H), 2.33 (s, 3H), 1.45–1.40 ( m, 6H). ¹³ C NMR (101MHz, CDCl ₃ )δ168.6, 167.6, 147.7, 138.0, 137.1, 132.0, 131.0, 129.2, 128.8, 128.7, 128.0, 126.3, 124.7, 124.6, 124.0, 120., 6, 118.5, 115.7, 111.2, 61.3, 61.2, 19.0, 14.4, 14.4, 13.5. HRMS: [M+Na] ⁺ calculated for _C26H22FNNaO5 ⁺ : _470.1374 , found: _470.1371 .

Example 4

Under nitrogen, 3-arylbenzoxazine compound 1d (0.20 mmol), diazo compound 2a (0.44 mmol), [Cp*RhCl ₂ ] ₂ (4 mol %), AgSbF ₆ (16 mol %), MesCOOH (0.4mmol) and solvent DCE (2.0mL) were added to a 10mL sealed tube, and reacted in a reaction module at 80 degrees for 10h. After the reaction was completed, the solvent was removed under reduced pressure, and the target product 8-chloro-5,12 was obtained by separation with a silica gel column. - Diethylisoquinoline[2,1,8-mna]phenoxazine-4,13-dicarboxylate (3da), all eluents were petroleum ether, ethyl acetate and dichloromethane as per 30 : 1:1 ratio is formulated. Characterization of product data: tan solid, 82% yield, melting range: 127-128°C. The NMR spectra of the products are shown in Figures 7 and 8, ¹ H NMR (400MHz, CDCl ₃ )δ7.21(d, J=8.6Hz, 1H), 7.15-7.06(m, 1H), 6.98-6.89(m, 2H), 6.74(t, J=7.6Hz, 2H), 4.46-4.36(m, 4H), 2.30(s, 3H), 2.29(s, 3H), 1.43-1.38(m, 6H). ¹³ C NMR (101MHz, CDCl ₃ ) ¹³ C NMR (101 MHz, CDCl ₃ ) δ 168.6, 167.7, 151.2, 138.0, 136.8, 131.1, 130.9, 129.2, 128.9, 128.6, 128.1, 125.9, 124.9, 124.0, 123.9, 17.9.4 , 117.3, 115.6, 61.4, 61.2, 19.0, 14.5, 14.4, 13.3. HRMS: [M+H] ⁺ calculated for C ₂₆ H ₂₃ ClNO ₅ ⁺ : 464.1259, found: 464.1244.

Example 5

Under nitrogen, 3-arylbenzoxazine compound 1e (0.20 mmol), diazo compound 2a (0.44 mmol), [Cp*RhCl ₂ ] ₂ (4 mol %), AgSbF ₆ (16 mol %), MesCOOH (0.4mmol) and solvent DCE (2.0mL) were added into a 10mL sealed tube, and reacted in a reaction module at 80 degrees for 10h. After the reaction was completed, the solvent was removed under reduced pressure, and the target product 8-bromo-5,12 was obtained by separation with a silica gel column. - Diethylisoquinoline[2,1,8-mna]phenoxazine-4,13-dicarboxylate (3ea), all eluents were petroleum ether, ethyl acetate and dichloromethane as per 30 : 1:1 ratio is formulated. Product Data Characterization: Yellow solid, 89% yield, melting range: 144-145°C. The NMR spectra of the products are shown in Figures 9 and 10, ¹ H NMR (400MHz, CDCl ₃ ) δ 7.20 (d, J=8.6 Hz, 1H), 7.13-7.00 (m, 3H), 6.74 (d, J= 7.2Hz, 1H), 6.64 (d, J=8.4Hz, 1H), 4.46–4.35 (m, 4H), 2.28 (s, 3H), 2.27 (s, 3H), 1.40 (td, J=7.1, 5.2 Hz, 6H). ¹³ C NMR (101MHz, CDCl ₃ )δ168.5, 167.6, 151.2, 137.9, 136.8, 130.8, 129.6, 128.8, 128.5, 127.9, 126.9, 125.8, 124.8, 123.9, 120.4, 120.4, 120.2, 117.3, 115.6, 61.3, 61.2, 18.9, 14.4, 14.4, 13.2. HRMS: [M+Na] ⁺ calculated for C ₂₆ H ₂₂ BrNNaO ₅ ⁺ =530.0574, found: 530.0564.

Example 6

Under nitrogen, 3-arylbenzoxazine compound 1f (0.20 mmol), diazo compound 2a (0.44 mmol), [Cp*RhCl ₂ ] ₂ (4 mol %), AgSbF ₆ (16 mol %), MesCOOH (0.4mmol) and solvent DCE (2.0mL) were added into a 10mL sealed tube, and reacted in a reaction module at 80 degrees for 10h. After the reaction was completed, the solvent was removed under reduced pressure, and the target product 8-methyl-5 was obtained by separation with a silica gel column. Diethyl 12-dimethylisoquinoline[2,1,8-mna]phenoxazine-4,13-dicarboxylate (3fa), all eluents were petroleum ether, ethyl acetate and dichloromethane It is formulated in a ratio of 30:1:1. Characterization of product data: yellow solid, 77% yield, melting range: 100-101°C. The NMR spectra of the product are shown in Figures 11 and 12, ¹ H NMR (400MHz, CDCl ₃ ) δ 7.18 (d, J=8.6Hz, 1H), 7.08 (t, J=8.0Hz, 1H), 6.78-6.68 (m, 4H), 4.48–4.34(m, 4H), 2.31(s, 3H), 2.31(s, 3H), 2.26(s, 3H), 1.40(td, J=7.1, 3.7Hz, 6H). ¹³ C NMR (101MHz, CDCl ₃ )δ168.8,168.0,150.6,139.0,137.1,136.1,131.4,129.3,128.4,127.8,127.5,125.9,125.1,124.4,123.4,120.0,111.2.4,117.9 , 61.0, 20.7, 19.2, 14.5, 14.4, 13.3. HRMS: [M+Na] ⁺ calculated for C ₂₇ H ₂₅ NNaO ₅ ⁺ =466.1625, found: 466.1617.

Example 7

Under nitrogen, 3-arylbenzoxazine compound 1 g (0.20 mmol), diazo compound 2a (0.44 mmol), [Cp*RhCl ₂ ] ₂ (4 mol %), AgSbF ₆ (16 mol %), MesCOOH (0.4mmol) and solvent DCE (2.0mL) were added into a 10mL sealed tube, and reacted in a reaction module at 80 degrees for 10h. After the reaction was completed, the solvent was removed under reduced pressure, and the target product 9-bromo-5,12 was obtained by separation with a silica gel column. - Diethylisoquinoline[2,1,8-mna]phenoxazine-4,13-dicarboxylate (3ga), all eluents were petroleum ether, ethyl acetate and dichloromethane as per 30 : 1:1 ratio is formulated. Product Data Characterization: Yellow solid, 91% yield, melting range: 132-133°C. The NMR spectra of the products are shown in Figures 13 and 14, ¹ H NMR (400 MHz, CDCl ₃ ) δ 7.21 (d, J=8.6 Hz, 1H), 7.13-7.08 (m, 2H), 6.94 (d, J= 1.6Hz, 1H), 6.77–6.74 (m, 2H), 4.45–4.37 (m, 4H), 2.31 (s, 3H), 2.30 (s, 3H), 1.43–1.39 (m, 6H). ¹³ C NMR (101MHz, CDCl ₃ )δ168.6,167.6,149.8,137.6,137.1,131.8,130.7,128.7,128.4,128.4,128.0,125.9,124.8,124.2,122.3,120.6,118.3,117.9,116.6.3 18.9, 14.5, 14.4, 13.3. HRMS: [M+H] ⁺ calculated for C ₂₆ H ₂₃ BrNO ₅ ⁺ = 508.0754, found: 508.0747.

Example 8

Under nitrogen, 3-arylbenzoxazine compound 1h (0.20 mmol), diazo compound 2a (0.44 mmol), [Cp*RhCl ₂ ] ₂ (4 mol %), AgSbF ₆ (16 mol %), MesCOOH (0.4 mmol) and solvent DCE (2.0 mL) were added to a 10 mL sealed tube, and reacted in a reaction module at 80 degrees for 10 h. After the reaction, the solvent was removed under reduced pressure, and the target product 9-methoxy-5 was obtained by separation with a silica gel column. ,12-Dimethylisoquinoline[2,1,8-mna]phenoxazine-4,13-dicarboxylate diethyl ester (3ha), all eluents were petroleum ether ethyl acetate and dichloromethane It is formulated according to the ratio of 30:1:1. Product Data Characterization: Yellow solid, 53% yield, melting range: 162-163°C. The NMR spectra of the products are shown in Figures 15 and 16, ¹ H NMR (400 MHz, CDCl ₃ ) δ 7.20 (d, J=8.3 Hz, 1H), 7.14-7.04 (m, 1H), 6.80 (d, J= 8.8Hz, 1H), 6.74 (d, J=7.0Hz, 1H), 6.52 (dd, J=8.8, 2.6Hz, 1H), 6.39 (d, J=2.7Hz, 1H), 4.46–4.36 (m, 4H), 2.34(s, 3H), 2.31(s, 3H), 1.42–1.38(m, 6H). ¹³ C NMR (101 MHz, CDCl ₃ ) δ 168.7, 167.8, 156.2, 144.2, 138.4, 137.6, 131.0, 130.9 ,128.9,128.2,127.6,125.9,125.0,123.7,120.3,117.0,115.3,109.4,106.6,61.2,61.1,55.9,19.2,14.4,14.4,13.3.HRMS: [M+H] ⁺ calculated for C ₂₇ H ₂₆ NO ₆ ⁺ = 460.1755, found: 460.1753.

Example 9

Under nitrogen, 3-arylbenzoxazine compound 1i (0.20 mmol), diazo compound 2a (0.44 mmol), [Cp*RhCl ₂ ] ₂ (4 mol %), AgSbF ₆ (16 mol %), MesCOOH (0.4mmol) and solvent DCE (2.0mL) were added to a 10mL sealed tube, and reacted in a reaction module at 80 degrees for 10h. After the reaction, the solvent was removed under reduced pressure, and the target product 2-fluoro-5,12 was obtained by separation with a silica gel column. - Diethylisoquinoline[2,1,8-mna]phenoxazine-4,13-dicarboxylate (3ia), all eluents were petroleum ether, ethyl acetate and dichloromethane as per 30 : 1:1 ratio is formulated. Characterization of product data: yellow solid, 82% yield, melting range: 162-163°C. The NMR spectra of the products are shown in Figures 17 and 18, ¹ H NMR (400 MHz, CDCl ₃ ) δ 7.07-7.03 (m, 1H), 7.00-6.96 (m, 1H), 6.92 (dd, J=7.9, 1.5 Hz, 1H), 6.88 (dd, J=11.4, 2.0Hz, 1H), 6.85 (dd, J=8.0, 1.2Hz, 1H), 6.61 (dd, J=10.2, 2.0Hz, 1H), 4.46–4.37 (m,4H), 2.37(s,3H), 2.32(s,3H), 1.43–1.39(m,6H). ¹³ C NMR (101 MHz, CDCl ₃ ) δ 168.2, 167.1, 162.6 (d, J=243.1 Hz ( d, J=29.2Hz), 103.8 (d, J=24.6Hz), 61.2, 61.2, 19.4, 14.4, 14.3, 13.4. HRMS: [M+H] ⁺ calculated for C ₂₆ H ₂₃ FNO ₅ ⁺ =448.1555, found: 448.1539.

Example 10

Under nitrogen, 3-arylbenzoxazine compound 1j (0.20 mmol), diazo compound 2a (0.44 mmol), [Cp*RhCl ₂ ] ₂ (4 mol %), AgSbF ₆ (16 mol %), MesCOOH (0.4mmol) and solvent DCE (2.0mL) were added into a 10mL sealed tube, and reacted in a reaction module at 80 degrees for 10h. After the reaction, the solvent was removed under reduced pressure, and the target product 2-bromo-5,12 was obtained by separation with a silica gel column. - Diethylisoquinoline[2,1,8-mna]phenoxazine-4,13-dicarboxylate (3ja), all eluents were petroleum ether, ethyl acetate and dichloromethane as per 30 : 1:1 ratio is formulated. Product Data Characterization: Yellow solid, 87% yield, melting range: 142-143°C. The NMR spectra of the products are shown in Figures 19 and 20, ¹ H NMR (400MHz, CDCl ₃ )δ7.39d, J=1.5Hz, 1H), 7.10-7.05(m,1H), 7.03-7.01(m,1H) ,6.94(dd,J=7.8,1.5Hz,1H),6.89-6.84(m,2H),4.49-4.39(m,4H),2.38(s,3H),2.34(s,3H),1.45-1.42 (m, 6H). ¹³ C NMR (101MHz, CDCl ₃ ) δ 168.1, 167.2, 150.7, 140.5, 137.4, 131.3, 131.0, 129.7, 129.4, 127.0, 126.3, 124.2, 123.6, 122.8, 122.1, 120.0, 118.4 ,115.4,77.2,61.4,61.3,19.4,14.4,14.4,13.4.HRMS: [M+H] ⁺ calculated for C ₂₆ H ₂₃ BrNO ₅ ⁺ =508.0754, found: 508.0742.

Example 11

Under nitrogen, 3-arylbenzoxazine compound 1k (0.20 mmol), diazo compound 2a (0.44 mmol), [Cp*RhCl ₂ ] ₂ (4 mol %), AgSbF ₆ (16 mol %), MesCOOH (0.4mmol) and solvent DCE (2.0mL) were added to a 10mL sealed tube, and reacted in a reaction module at 80 degrees for 10h. After the reaction, the solvent was removed under reduced pressure, and the target product 2-methoxy-5 was obtained by separation with a silica gel column. ,12-Dimethylisoquinoline[2,1,8-mna]phenoxazine-4,13-dicarboxylate (3ka), all eluents were petroleum ether ethyl acetate and dichloromethane It is formulated according to the ratio of 30:1:1. Characterization of product data: red solid, 77% yield, melting range: 172-173°C. The NMR spectra of the product are shown in Figures 21 and 22, ¹ H NMR (400MHz, CDCl ₃ ) δ 7.52 (s, 1H), 7.08 (t, J=7.7Hz, 1H), 7.03-6.99 (m, 1H) ,6.95–6.93(m,2H),6.88–6.86(d,J=7.4Hz,1H),4.49(q,J=7.1Hz,1H),4.43(q,J=7.2Hz,1H),2.39( s, 3H), 2.36 (s, 3H), 1.45–1.41 (m, 6H). ¹³ C NMR (101 MHz, CDCl ₃ ) δ 167.9, 167.2, 150.5, 140.9, 138.7, 131.1, 130.7, 129.7 (q, J= 31.8Hz), 129.5, 127.3, 126.3, 126.2, 124.7, 124.3, 124.2 (q, J=272.7Hz), 120.0, 117.7 (dd, J=9.2), 117.7 (d, J=4.7Hz), 117.4, 115.7 ,110.8(d,J=3.2Hz).61.5,61.3,19.5,14.3,14.3,13.3.HRMS: [M+H] ⁺ calculated for C ₂₇ H ₂₃ F ₃ NO ₅ ⁺ =498.1523, found: 498.1508.

Example 12

Under nitrogen, 3-arylbenzoxazine compound 1a (0.20 mmol), diazo compound 2b (0.44 mmol), [Cp*RhCl ₂ ] ₂ (4 mol %), AgSbF ₆ (16 mol %), MesCOOH (0.4 mmol) and solvent DCE (2.0 mL) were added into a 10 mL sealed tube, and reacted in a reaction module at 80 degrees for 10 h. After the reaction, the solvent was removed under reduced pressure, and the target product 5,12-dimethyl was obtained by separation with a silica gel column. Dipentyl isoquinoline[2,1,8-mna]phenoxazine-4,13-dicarboxylate (3ab), all eluents were petroleum ether, ethyl acetate and dichloromethane at 30:1:1 proportions are prepared. Product data characterization: yellow liquid, 96% yield. The NMR spectra of the products are shown in Figures 23 and 24, ¹ H NMR (400 MHz, CDCl ₃ ) δ 7.23-7.15 (m, 1H), 7.09 (t, J=7.9 Hz, 1H), 7.03 (t, J= 7.4Hz, 1H), 6.99–6.95 (m, 1H), 6.91 (dd, J=7.7, 1.6Hz, 1H), 6.84 (d, J=7.7Hz, 1H), 6.79–6.67 (m, 1H), 4.36(t,J＝6.7Hz,3H),4.31(t,J＝6.8Hz,3H),2.32(s,3H),2.31(s,3H),1.80–1.73(m,4H),1.43–1.36 (m, 8H), 0.95–0.90 (m, 6H). ¹³ C NMR (101 MHz, CDCl ₃ ) δ 168.9, 168.0, 150.7, 138.6, 137.2, 131.3, 130.3, 129.2, 128.4, 127.8, 125.9, 125.8, 125.1, 124.0,123.7,120.2,119.7,117.2,116.9,115.3,65.4,65.3,28.5,28.4,28.3,28.3,22.4,22.4,19.1,14.1,14.1,13.3.HRMS: [M+H] ⁺ calculated for C ₃₂ H ₃₆ NO ₅ ⁺ =514.2588, found: 514.2577.

Example 13

Under nitrogen, 3-arylbenzoxazine compound 1a (0.20 mmol), diazo compound 2c (0.44 mmol), [Cp*RhCl ₂ ] ₂ (4 mol %), AgSbF ₆ (16 mol %), MesCOOH (0.4 mmol) and solvent DCE (2.0 mL) were added into a 10 mL sealed tube, and reacted in a reaction module at 80 degrees for 10 h. After the reaction, the solvent was removed under reduced pressure, and the target product 5,12-dimethyl was obtained by separation with a silica gel column. Diisopropyl isoquinoline[2,1,8-mna]phenoxazine-4,13-dicarboxylate (3ac), all eluents were petroleum ether, ethyl acetate and dichloromethane at 30:1: 1 in the ratio. Product data characterization: red liquid, 80% yield. The NMR spectra of the products are shown in Figures 25 and 26, ¹ H NMR (400MHz, CDCl ₃ )δ7.24(d, J=23.1Hz, 1H), 7.16-7.07(m, 1H), 7.02-6.89(m, 3H), 6.84–6.80 (m, 1H), 6.75–6.70 (m, 1H), 5.39–5.28 (m, 2H), 2.33 (s, 6H), 1.44–1.36 (m, 12H). ¹³ C NMR( 101MHz, CD Cl ₃ )δ168.1, 167.2, 150.5, 137.9, 137.1, 131.1, 130.2, 129.1, 128.2, 127.7, 125.6, 125.4, 125.0, 123.9, 119.9, 119.5, 117.1, 114.9, 68.7, 68.8, 18.9, 13.1. HRMS: [M+H] ⁺ calculated for C ₂₈ H ₂₈ NO ₅ ⁺ = 458.1962, found: 458.1943.

Example 14

Under nitrogen, 3-arylbenzoxazine compound 1a (0.20 mmol), diazo compound 2d (0.44 mmol), [Cp*RhCl ₂ ] ₂ (4 mol %), AgSbF ₆ (16 mol %), MesCOOH (0.4 mmol) and solvent DCE (2.0 mL) were added to a 10 mL sealed tube, and reacted in a reaction module of 80 degrees for 10 h. After the reaction, the solvent was removed under reduced pressure, and the target product 5,12-diethyl was obtained by separation with a silica gel column. Dimethyl isoquinoline[2,1,8-mna]phenoxazine-4,13-dicarboxylate (3ad), all eluents were petroleum ether, ethyl acetate and dichloromethane 30:1:1 proportions are prepared. Product data characterization: yellow liquid, 60% yield. The NMR spectra of the products are shown in Figures 27 and 28, ¹ H NMR (400MHz, CDCl ₃ )δ7.17(t, J=8.5Hz, 1H), 7.13-7.08(m, 1H), 7.07-7.03(m, 1H), 7.01–6.95 (m, 1H), 6.94–6.88 (m, 2H), 6.70 (d, J=7.1Hz, 1H), 3.94 (s, 3H), 3.91 (s, 3H), 2.81–2.74 (m, 2H), 2.69 (dd, J=8.7, 6.8Hz, 2H), 1.71–1.52 (m, 4H), 0.99 (t, J=7.4Hz, 3H), 0.94 (t, J=7.3Hz, 3H). ¹³ C NMR (101MHz, CDCl ₃ )δ169.3, 168.5, 150.7, 142.8, 137.4, 132.2, 131.6, 130.9, 129.0, 128.5, 127.8, 125.7, 124.9, 124.1, 123.1, 120.8, 117.3, 3, 1 115.6, 52.2, 52.2, 32.4, 30.2, 23.9, 22.8, 14.5, 13.9. HRMS: [M+H] ⁺ calculated for C ₂₈ H ₂₈ NO ₅ ⁺ =458.1962, found: 458.1949.

Example 15

Under nitrogen, 3-arylbenzoxazine compound 1a (0.20 mmol), diazo compound 2e (0.44 mmol), [Cp*RhCl ₂ ] ₂ (4 mol %), AgSbF ₆ (16 mol %), MesCOOH (0.4mmol) and solvent DCE (2.0mL) were added to a 10mL sealed tube, and reacted in a reaction module at 80 degrees for 10h. After the reaction was completed, the solvent was removed under reduced pressure, and the target product 5,12-dipropyl was obtained by separation with a silica gel column. Dimethyl isoquinoline[2,1,8-mna]phenoxazine-4,13-dicarboxylate (3ae), all eluents were petroleum ether, ethyl acetate and dichloromethane 30:1:1 proportions are prepared. Product data characterization: yellow liquid, 63% yield. The NMR spectra of the products are shown in Figures 29 and 30, ¹ H NMR (400MHz, CDCl ₃ ) δ 7.19 (dd, J=8.6, 0.7 Hz, 1H), 7.13-7.09 (m, 1H), 7.07-7.03 ( m, 1H), 7.00–6.96 (m, 1H), 6.93 (dd, J=7.8, 1.5Hz, 0H), 6.90 (dd, J=7.9, 1.4Hz, 1H), 6.70 (dd, J=7.2, 0.7Hz, 1H), 3.94 (s, 3H), 3.91 (s, 3H), 2.82–2.79 (m, 2H), 2.76–2.65 (m, 2H), 1.65–1.51 (m, 4H), 1.48–1.39 (m, 2H), 1.37–1.32 (m, 2H), 0.96 (t, J=7.3Hz, 3H), 0.85 (t, J=7.3Hz, 3H). ¹³ C NMR (101MHz, CDCl ₃ )δ169. 3,168.5,150.7,143.1,137.4,132.2,131.6,131.2,129.1,128.5,127.7,125.7,124.8,124.1,123.0,120.7,111.3,118.1,117.2,115.5,52.2,9.7,30.1 23.0, 22.4, 14.1, 13.8. HRMS: [M+H] ⁺ calculated for C ₃₀ H ₃₂ NO ₅ ⁺ = 486.2275, found: 486.2266.

The above descriptions are only preferred embodiments of the present invention, and are not intended to limit the present invention. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the scope of the present invention. within the scope of protection.

Claims (10)

1. A nitrogen and oxygen fused ring aromatic hydrocarbon is characterized in that the structural formula is as follows:

wherein R is any one of H, Me, OMe, F, Cl or Br; r¹Any one of Me, n-Pr or Ph; r²Is n-Am orⁱPr; ar is Me, OMe, F, Cl, Br, Ph or CF₃Any substituted benzene ring.

2. A process for the synthesis of nitrogen and oxa-fused ring aromatic hydrocarbons as claimed in claim 1, comprising the steps of: adding an oxazine compound 1, a diazo compound 2, a catalyst and an additive into a solvent in an inert atmosphere for reaction to obtain a hetero-condensed ring aromatic compound 3 after the reaction is finished, wherein the reaction equation is as follows:

wherein R is any one of H, Me, OMe, F, Cl or Br; r¹Any one of Me, n-Pr or Ph; r²Is n-Am orⁱPr；Ar is Me, OMe, F, Cl, Br, Ph or CF₃Any substituted benzene ring.

3. The method for synthesizing nitrogen-and oxa-condensed ring aromatic hydrocarbons according to claim 2, wherein: the reaction temperature is 80-120 ℃ in the reaction process, and the reaction time is 6-12 h.

4. A method for synthesizing nitrogen-and oxa-condensed ring aromatic hydrocarbons according to claim 2 or 3, wherein: the catalyst comprises a rhodium catalyst and a silver salt; the molar ratio of rhodium catalyst to silver salt is 1: 4; the rhodium catalyst is any one or combination of dichloro (pentamethylcyclopentadienyl) rhodium dimer, pentamethylcyclopentadienyl rhodium acetate or bis (hexafluoroantimonate) triethylenenitrile (pentamethylcyclopentadienyl) rhodium; the silver salt is any one or combination of silver hexafluoroantimonate, silver tetrafluoroborate, silver bistrifluoromethanesulfonimide, silver trifluoromethanesulfonate, silver sulfate, silver acetate and silver trifluoroacetate.

5. The method for synthesizing nitrogen-and oxa-condensed ring aromatic hydrocarbons according to claim 4, wherein: the catalyst consists of dichloro (pentamethyl cyclopentadienyl) rhodium dimer and silver hexafluoroantimonate; the molar ratio of dichloro (pentamethylcyclopentadienyl) rhodium dimer to silver hexafluoroantimonate was 1: 4.

6. the method for synthesizing nitrogen-and oxa-condensed ring aromatic hydrocarbons according to claim 5, wherein: the additive is any one or combination of 2,4, 6-trimethyl benzoic acid, pivalic acid, acetic acid, 1-adamantane formic acid, zinc acetate, sodium carbonate, potassium acetate or potassium carbonate.

7. The method for synthesizing nitrogen-and oxa-condensed ring aromatic hydrocarbons according to claim 6, wherein: the solvent is any one or combination of dichloroethane, methanol, acetonitrile, 1,4-dioxane or toluene.

8. A method of synthesizing nitrogen and oxa-polycyclic aromatic hydrocarbons according to any one of claims 5 to 7, wherein: the inert atmosphere is nitrogen atmosphere.

9. The method as recited in claim 8, wherein the nitrogen-and oxygen-containing condensed ring aromatic hydrocarbon is synthesized by: the molar ratio of the oxazine compound 1, the diazo compound 2, the catalyst, the additive and the solvent is as follows: 1:(2-3):(0.02-0.04):(0.08-0.16).

10. The method for synthesizing nitrogen-and oxa-condensed ring aromatic hydrocarbons according to claim 9, wherein: the concentration of the reaction system in the solvent is 0.05M-0.2M.

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