Method for constructing carbon-carbon bond based on carbon-halogen bond on aromatic ring

Abstract

The invention discloses a method for constructing a carbon-carbon bond based on a carbon-halogen bond on an aromatic ring. The method comprises the following steps: dissolving an electron-deficient substrate containing a carbon halogen bond in a solvent to obtain a solution A; adding an electron-rich substrate and an alkaline compound into the solution A to obtain a solution B; and heating the solution B in an atmospheric environment, and completing the construction of carbon-carbon bonds through a coupling reaction. According to the method, strong charge transfer interaction between two substrates is utilized, carbon-carbon bonds on aromatic rings are successfully constructed at a proper temperature and under the participation of an alkaline compound, the used reaction substrates do not need to be subjected to pre-functional group modification, the synthesis process is greatly simplified, in addition, inert gas protection, illumination and deliberate light shielding are not needed in the reaction process, and the method is suitable for industrial production. The method has the advantages of simple operation, low reaction environment requirements, simple reaction operation, wide substrate application range, mild reaction conditions and the like, and the obtained coupling product can be used as a reaction raw material and has a wide application prospect in preparation of fluorescent dyes, photoelectric materials and the like.

Description

Technical Field

[0001] The present invention relates to the field of coupling reactions. More specifically, it relates to a method for constructing carbon-carbon bonds based on carbon-halogen bonds on an aromatic ring. Background Art

[0002] Aromatic ring structures are widely present in natural products, drug molecules, and various functional materials. Connecting aromatic ring moieties can yield a variety of functional molecules. Among them, carbon-carbon coupling reactions are important tools for realizing the connection of aromatic ring moieties. In the past few decades, various coupling reactions have been developed for constructing carbon-carbon bonds. Most of these reactions require the participation of metal catalysts. For example, the Ullmann reaction involving metal copper, the Kumada reaction involving metal nickel, the Suzuki reaction and the Stille reaction involving metal palladium, etc. Some reactions even require pre-functional group modification of the reaction substrates. For example, the boric acid or borate group in the Suzuki coupling reaction. Although the transition metal-catalyzed carbon-carbon coupling reactions have developed vigorously, there are still many problems in practical applications. For example, the transition metal catalysts are expensive, the reaction conditions are harsh, and the reaction substrates require complex pre-functional group modification. Therefore, it is of great significance to develop a metal-free catalytic carbon-carbon coupling method. Summary of the Invention

[0003] The purpose of the present invention is to provide a method for constructing carbon-carbon bonds based on carbon-halogen bonds on an aromatic ring. This method can construct carbon-carbon bonds from carbon-halogen bonds on an aromatic ring through a coupling reaction, providing a new synthetic route for technicians. At the same time, the reaction process does not require inert gas protection, light irradiation, or deliberate light avoidance, has low requirements for the reaction environment, and the obtained coupling products can be used as reaction raw materials and have broad application prospects in the preparation of fluorescent dyes, optoelectronic materials, etc.

[0004] To achieve the above purpose, the present invention adopts the following technical solutions:

[0005] The present invention discloses a method for constructing carbon-carbon bonds based on carbon-halogen bonds on an aromatic ring, comprising the following steps:

[0006] Dissolve an electron-deficient substrate containing a carbon-halogen bond in a solvent to obtain solution A;

[0007] Add an electron-rich substrate and a basic compound to solution A to obtain solution B;

[0008] Heat solution B under an atmospheric environment to complete the construction of carbon-carbon bonds through a coupling reaction;

[0009] Wherein, the electron-deficient substrate is selected from one of the following general formula structures:

[0010]

[0011] wherein X represents H, F, Cl, Br or NO 2 , and at least one X in the electron-deficient substrate represents F, Cl or Br;

[0012] wherein Y represents O, S, Se or CR 3 R 4 wherein R 3 and R 4 may be the same or different and each independently represents H or an alkyl group having 1 to 3 carbon atoms;

[0013] In the structure of formula I, R 1 and R 2 may be the same or different and each independently represents H or NO 2 , and when both R 1 and R 2 are H, at least one X in the electron-deficient substrate represents NO 2 ;

[0014] The electron-rich substrate is selected from nitrogen-containing aromatic hydrocarbons.

[0015] Due to strong intermolecular charge transfer interactions, the electron-deficient substrate and the electron-rich substrate will form a charge transfer complex in solution B. The formation of the complex brings the two substrate molecules closer together, reduces the activation energy barrier, and is conducive to further reaction. Then, part of the charge on the electron-rich substrate is transferred to the electron-deficient substrate, sharing a carbon atom with the halogen group in the structure of the electron-deficient substrate to form an zwitterionic intermediate, initially forming a carbon-carbon bond. After that, the halogen group leaves, and with the participation of a basic compound, the proton on the electron-rich substrate also leaves to obtain the final coupling product. The reaction mechanism can be seen in Figure 1 .

[0016] Furthermore, the electron-deficient substrate is selected from one or more of the following structures:

[0017]

[0018] Furthermore, the electron-rich substrate is selected from one or more of the following structures, and its reaction site is on the carbon atom of the benzene ring:

[0019]

[0020] Furthermore, the basic compound is selected from one or more of sodium carbonate, cesium carbonate, potassium carbonate, triethylamine, and N,N-diisopropylethylamine.

[0021] Furthermore, the reaction temperature of the coupling reaction is 25 - 100 °C, preferably 50 - 100 °C, and the reaction time is 5 min - 96 h.

[0022] The electron-deficient substrates provided by the present invention include structures containing one carbon-halogen bond and structures containing multiple carbon-halogen bonds. Through a large number of experiments, it has been found that for those structures containing multiple carbon-halogen bonds, based on the method provided by the present invention, the mono-substituted product and the multi-substituted product can be selectively prepared by controlling the type of basic compound. More specifically, when the basic compound is selected from relatively weak bases such as sodium carbonate, potassium carbonate, triethylamine, N,N-diisopropylethylamine, etc., only the mono-substituted product with high yield will be generated, and halogen atoms still remain in the product, which provides the possibility for further structural modification and conditions for the development of compounds with diverse structures and asymmetric structures. When the basic compound is selected from stronger bases such as cesium carbonate, the mono-substituted product can be further reacted to generate multi-substituted products (such as bis-substituted products, tris-substituted products, etc.) by extending the reaction time. This method is more controllable than the traditional method of obtaining more mono-substituted products by controlling the feed ratio, and eliminates the problem of low yield of mono-substituted products caused by the generation of multi-substituted products.

[0023] Further, the molar ratio of the electron-deficient substrate to the electron-rich substrate is 1:0.2 - 5.

[0024] Further, the solvent is selected from one or more of acetonitrile, dichloromethane, chloroform, and N,N-dimethylformamide.

[0025] Further, the concentration of the electron-deficient substrate in solution A is 6.5 mM to the saturation concentration.

[0026] Further, the concentration of the electron-rich substrate in solution B is 6.5 mM to the saturation concentration.

[0027] Further, the molar ratio of the electron-deficient substrate to the basic compound is 1:0.2 - 3.

[0028] The beneficial effects of the present invention are as follows:

[0029] The present invention discloses a method for constructing a carbon-carbon bond based on the carbon-halogen bond on an aromatic ring. This method utilizes the strong charge transfer interaction between two substrates to successfully construct the carbon-carbon bond on the aromatic ring under appropriate temperature and in the presence of a basic compound. The reaction substrates used do not need to be pre-functionalized, which greatly simplifies the synthesis process. In addition, the reaction process does not require inert gas protection, light irradiation, or deliberate light avoidance, and has low requirements for the reaction environment. It also has the advantages of simple reaction operation, wide substrate applicability, and mild reaction conditions. The obtained coupling product can be used as a reaction raw material and has broad application prospects in the preparation of fluorescent dyes, optoelectronic materials, etc.

[0030] By controlling the type of alkaline compound, the present invention further affects the selective generation of mono-substituted products or di-substituted products when a compound containing multiple carbon-halogen bonds is used as a reaction substrate. This not only enables the synthesis of symmetric and asymmetric structure molecules according to application requirements, providing conditions for the design of diverse structures, but also improves the yield of the target product. Description of the Drawings

[0031] Figure 1 Shows the reaction mechanism diagram of Example 1.

[0032] Figure 2 Shows the radical test diagram of Example 1.

[0033] Figure 3 Shows the dye spectrogram of Synthesis Examples 1-5; wherein, Figure 3 a is the absorption spectrogram and b is the emission spectrogram. Detailed Description of the Invention

[0034] To more clearly illustrate the present invention, the following further describes the present invention in conjunction with preferred embodiments and the drawings. Similar components in the drawings are denoted by the same reference numerals. Those skilled in the art should understand that the content specifically described below is illustrative rather than restrictive, and should not be used to limit the protection scope of the present invention.

[0035] Example 1

[0036] Under atmospheric conditions, 50 mg of Compound B was dissolved in 2 mL of acetonitrile solution, then 23 mg of Compound J and 14 mg of sodium carbonate were added thereto, and then heated to 80 °C and reacted for 6.5 h. After the reaction was completed, it was concentrated under reduced pressure and purified by column chromatography to obtain 57 mg of a dark blue solid compound with a yield of 92%. For the reaction mechanism diagram, see Figure 1 .

[0037] 1 H NMR(600MHz,CDCl 3 ,298K)δ7.00(s,2H),3.26(t,J=6.0Hz,4H),2.77(t,J=6.2Hz,4H),1.99(p,J=5.9Hz,4H).

[0038] 13 C NMR(150MHz,CDCl 3 ,298K)δ152.70,152.55,145.76,145.24,140.82,130.79,128.22,121.57,115.71,105.51,50.01,27.85,21.52.

[0039] HRMS(ESI) calculated for C 18 H 15 N 5 O 4 SBr + [M+H + : 476.0022, found 476.0028.

[0040]

[0041] The similar reactions reported in the existing relevant literature usually initiate single - electron transfer between reactants by means of light irradiation, thereby generating free - radical species and then the reaction occurs. The reaction provided by the present invention does not require the irradiation of an external light source to initiate, so the reaction mechanism is different from the free - radical mechanism in the literature, Figure 2 which is the detection result of the EPR signal during the reaction in Example 1. During this process, no free - radical signal was detected.

[0042] Example 2

[0043] Under an atmospheric environment, 50 mg of compound B was dissolved in 2 mL of acetonitrile solution, then 21 mg of compound a and 14 mg of sodium carbonate were added thereto, and then heated to 80 °C and reacted for 8 h. After the reaction was completed, it was concentrated under reduced pressure and purified by column chromatography to obtain 33 mg of a dark blue solid compound with a yield of 53%.

[0044] 1 H NMR(600 MHz, C 2 D 2 Cl 4 , 298 K) δ 7.27(dd, J = 8.6, 2.3 Hz, 1H), 7.17(d, J = 2.1 Hz, 1H), 6.67(d, J = 8.7 Hz, 1H), 3.43 - 3.35(m, 4H), 2.79(t, J = 6.1 Hz, 2H), 1.99(p, J = 6.2 Hz, 2H), 1.21(t, J = 7.1 Hz, 3H).

[0045] 13 C NMR(150 MHz, C 2 D 2 Cl 4 , 298 K) δ 152.38, 152.08, 147.05, 145.17, 140.28, 130.41, 129.97, 128.90, 122.48, 115.32, 110.04, 105.56, 48.33, 45.33, 27.90, 21.45, 11.20.

[0046] HRMS(ESI) calculated for C 17 H 15 N 5 O 4 SBr + [M + H + 464.0022, found 464.0027.

[0047]

[0048] Example 3

[0049] Under atmospheric conditions, 50 mg of Compound B was dissolved in 2 mL of acetonitrile solution, then 23 mg of Compound b and 14 mg of sodium carbonate were added thereto, and then heated to 80 °C and reacted for 30 h. After the reaction was completed, it was concentrated under reduced pressure and purified by column chromatography to obtain 28 mg of a dark blue solid compound with a yield of 45%.

[0050] 1 H NMR (600 MHz, C 2 D 2 Cl 4 , 298 K) δ 7.26 (dd, J = 8.6, 2.3 Hz, 1H), 7.17 (d, J = 2.1 Hz, 1H), 6.76 (d, J = 8.7 Hz, 1H), 3.88 (q, J = 5.5 Hz, 2H), 3.54 (t, J = 5.7 Hz, 2H), 3.48 - 3.43 (m, 2H), 2.82 (t, J = 6.2 Hz, 2H), 2.01 (p, J = 6.2 Hz, 2H).

[0051] 13 C NMR (100 MHz, C 2 D 2 Cl 4 , 298 K) δ 152.36, 152.04, 147.58, 145.04, 140.56, 130.22, 130.08, 128.72, 122.72, 116.14, 110.61, 106.13, 59.74, 53.30, 50.24, 27.85, 21.46.

[0052] HRMS(ESI) calculated for C 17 H 15 N 5 O 5 SBr + [M + H + 479.9971, found 479.9978.

[0053]

[0054] Example 4

[0055] Under atmospheric conditions, 50 mg of Compound B was dissolved in 2 mL of acetonitrile solution. Then, 17 μL of Compound c and 14 mg of sodium carbonate were added thereto, and the mixture was heated to 80 °C and reacted for 77 h. After the reaction was completed, it was concentrated under reduced pressure and purified by column chromatography to obtain 10 mg of a dark purple solid compound with a yield of 17%.

[0056] 1 H NMR(400MHz,CDCl 3 ,298K)δ7.46(d,J=9.0Hz,2H),6.80(d,J=9.0Hz,2H),3.07(s,6H).

[0057] 13 C NMR(150MHz,CDCl 3 ,298K)δ152.71,152.48,151.87,145.58,141.42,130.64,130.45,116.72,112.17,106.59,40.19.

[0058] HRMS(ESI)calculated for C 14 H 11 N 5 O 4 SBr + [M+H + 423.9707,found 423.9707.

[0059]

[0060] Example 5

[0061] Under atmospheric conditions, 50 mg of Compound B was dissolved in 2 mL of acetonitrile solution. Then, 21 μL of Compound d and 14 mg of sodium carbonate were added thereto, and the mixture was heated to 80 °C and reacted for 77 h. After the reaction was completed, it was concentrated under reduced pressure and purified by column chromatography to obtain 25 mg of a dark purple solid compound with a yield of 41%.

[0062] 1 H NMR(600MHz,CDCl 3 ,298K)δ7.44(d,J=9.0Hz,2H),6.76(d,J=8.9Hz,2H),3.43(q,J=7.1Hz,4H),1.22(t,J=7.1Hz,6H).

[0063] 13 C NMR (100 MHz, CDCl 3 , 298 K) δ 152.72, 152.47, 149.66, 141.10, 130.99, 130.47, 121.40, 115.76, 111.54, 106.08, 44.57, 12.69.

[0064] HRMS (ESI) calculated for C 16 H 15 N 5 O 4 SBr + [M + H + 452.0022, found 452.0026.

[0065]

[0066] Example 6

[0067] Under atmospheric conditions, 50 mg of Compound B was dissolved in 2 mL of acetonitrile solution, then 23 μL of Compound e and 14 mg of sodium carbonate were added thereto, and then heated to 80 °C and reacted for 42 h. After the reaction was completed, it was concentrated under reduced pressure and purified by column chromatography to obtain 23 mg of a dark purple solid compound with a yield of 38%.

[0068] 1 H NMR (400 MHz, CDCl 3 , 298 K) δ 6.99 (d, J = 8.6 Hz, 1H), 6.60 (d, J = 2.3 Hz, 1H), 6.54 (dd, J = 8.6, 2.5 Hz, 1H), 3.39 (q, J = 7.1 Hz, 4H), 2.08 (s, 3H), 1.20 (t, J = 7.1 Hz, 6H).

[0069] 13 C NMR (150 MHz, CDCl 3 , 298 K) δ 152.99, 152.29, 149.45, 145.08, 143.50, 137.90, 131.82, 129.96, 115.70, 112.93, 109.08, 108.40, 44.36, 21.09, 12.77.

[0070] HRMS (ESI) calculated for C 17 H 17 N 5 O 4 SBr + [M + H +466.0179, found 466.0185.

[0071]

[0072] Example 7

[0073] Under an atmospheric environment, 50 mg of Compound B was dissolved in 2 mL of acetonitrile solution, 30 μL of Compound f and 14 mg of sodium carbonate were added thereto, and then the mixture was heated to 80 °C and reacted for 77 h. After the reaction was completed, it was concentrated under reduced pressure and purified by column chromatography to obtain 30 mg of a dark purple solid compound with a yield of 45%.

[0074] 1 H NMR (400 MHz, CDCl 3 , 298 K) δ 7.44 (d, J = 8.8 Hz, 2H), 6.72 (d, J = 8.7 Hz, 2H), 3.38 - 3.28 (m, 4H), 1.62 (p, J = 8.3, 7.8 Hz, 4H), 1.38 (h, J = 7.3 Hz, 7H), 0.98 (t, J = 7.3 Hz, 6H).

[0075] 13 C NMR (100 MHz, CDCl 3 , 298 K) δ 152.73, 152.47, 150.04, 145.70, 141.03, 130.92, 130.45, 115.65, 111.63, 105.99, 50.91, 29.43, 20.45, 14.09.

[0076] HRMS (ESI) calculated for C 20 H 23 N 5 O 4 SBr + [M + H + 508.0648, found 508.0657.

[0077]

[0078] Example 8

[0079] Under an atmospheric environment, 50 mg of Compound B was dissolved in 2 mL of acetonitrile solution, 22 μL of Compound g and 14 mg of sodium carbonate were added thereto, and then the mixture was heated to 80 °C and reacted for 5 min. After the reaction was completed, it was concentrated under reduced pressure and purified by column chromatography to obtain 47 mg of a dark blue solid compound with a yield of 77%.

[0080] 11H NMR (600 MHz, CDCl 3 , 298 K) δ 7.28 (d, J = 8.6 Hz, 1H), 6.50 (dd, J = 8.7, 2.5 Hz, 1H), 6.38 (d, J = 2.4 Hz, 1H), 3.06 (s, 6H), 2.42 (s, 6H).

[0081] 13 13C NMR (100 MHz, CDCl 3 , 298 K) δ 153.53, 152.96, 152.93, 152.85, 146.40, 140.61, 132.80, 131.02, 111.67, 106.46, 105.73, 102.75, 43.12, 40.25.

[0082] HRMS (ESI) calculated for C 16 H 16 N 6 O 4 SBr + [M + H + 467.0131, found 467.0137.

[0083]

[0084] Example 9

[0085] Under atmospheric conditions, 50 mg of Compound B was dissolved in 2 mL of acetonitrile solution. Then, 19 μL of Compound h and 14 mg of sodium carbonate were added thereto, and the mixture was heated to 80 °C and reacted for 7 h. After the reaction was completed, it was concentrated under reduced pressure and purified by column chromatography to obtain 51 mg of a dark purple solid compound with a yield of 86%.

[0086] 1 1H NMR (600 MHz, CDCl 3 , 298 K) δ 7.39 (d, J = 8.7 Hz, 1H), 6.47 (dd, J = 8.7, 2.3 Hz, 1H), 6.22 (d, J = 2.2 Hz, 1H), 3.69 (s, 3H), 3.08 (s, 6H).

[0087] 13 13C NMR (150 MHz, CDCl 3 , 298 K) δ 157.79, 153.63, 153.06, 152.82, 146.14, 141.82, 132.61, 128.72, 106.70, 106.43, 104.70, 94.77, 54.84, 40.39.

[0088] HRMS(ESI) calculated for C 15 H 13 N 5 O 5 SBr + [M + H + 453.9815, found 453.9804.

[0089]

[0090] Example 10

[0091] Under atmospheric conditions, 50 mg of Compound B was dissolved in 2 mL of acetonitrile solution, then 27 μL of Compound i and 14 mg of sodium carbonate were added thereto, and then heated to 80 °C and reacted for 96 h. After the reaction was completed, it was concentrated under reduced pressure and purified by column chromatography to obtain 10 mg of a dark purple solid compound with a yield of 25%.

[0092] 1 H NMR (400 MHz, C 2 D 2 Cl 4 , 298 K) δ 7.44 - 7.35 (m, 4H), 7.32 - 7.25 (m, 3H), 6.81 (d, J = 9.0 Hz, 2H), 4.62 (s, 2H), 3.57 (q, J = 7.0 Hz, 2H), 1.29 (d, J = 7.0 Hz, 3H).

[0093] 13 C NMR (150 MHz, C 2 D 2 Cl 4 , 298 K) δ 152.37, 151.98, 150.13, 145.04, 140.71, 137.75, 130.70, 130.06, 128.73, 127.09, 126.26, 116.22, 111.85, 106.36, 53.47, 45.26, 12.06.

[0094] HRMS(ESI) calculated for C 21 H 17 N 5 O 4 SBr + [M + H + 514.0179, found 514.0183.

[0095]

[0096] Example 11

[0097] Under an atmospheric environment, 50 mg of Compound B was dissolved in 2 mL of acetonitrile solution, then 19 mg of Compound j and 14 mg of sodium carbonate were added thereto, and then it was heated to 80 °C and reacted for 24 h. After the reaction was completed, it was concentrated under reduced pressure and purified by column chromatography to obtain 15 mg of a dark blue solid compound with a yield of 26%.

[0098] 1 H NMR(600MHz,C 2 D 2 Cl 4 ,298K)δ8.65(d,J=15.7Hz,1H),7.56(d,J=8.8Hz,2H),7.09(d,J=15.7Hz,1H),6.72(d,J=8.7Hz,2H),3.07(s,6H).

[0099] 13 C NMR(150MHz,C 2 D 2 Cl 4 ,298K)δ152.84,151.89,150.39,146.21,139.51,133.47,130.01,126.53,123.67,111.79,110.79,104.27,40.03.

[0100] HRMS(ESI)calculated for C 16 H 13 N 5 O 4 SBr + [M+H + 449.9866,found 449.9864.

[0101]

[0102] Example 12

[0103] Under an atmospheric environment, 50 mg of Compound B was dissolved in 2 mL of acetonitrile solution, then 19 mg of Compound k and 14 mg of sodium carbonate were added thereto, and then it was heated to 80 °C and reacted for 12 h. After the reaction was completed, it was concentrated under reduced pressure and purified by column chromatography to obtain 3 mg of a deep purple solid compound with a yield of 6%.

[0104] 1 H NMR(400MHz,C 2 D 2 Cl 4, 298 K) δ 7.61 (d, J = 8.9 Hz, 2H), 6.69 (d, J = 8.9 Hz, 2H), 3.08 (s, 6H).

[0105] 13 C NMR (151 MHz, CD 2 Cl 2 , 298 K) δ 152.52, 152.24, 152.07, 145.80, 142.38, 134.78, 129.70, 115.63, 114.76, 111.80, 106.62, 81.91, 39.98.

[0106] HRMS (ESI) calculated for C 16 H 11 N 5 O 4 SBr + [M + H + 447.9709, found 447.9700.

[0107]

[0108] Example 13

[0109] Under atmospheric conditions, 50 mg of Compound B was dissolved in 2 mL of acetonitrile solution, 16 μL of Compound I and 14 mg of sodium carbonate were added thereto, and then heated to 80 °C and reacted for 19 h. After the reaction was completed, it was concentrated under reduced pressure and purified by column chromatography to obtain 43 mg of a red solid with a yield of 78%.

[0110] 1 H NMR (600 MHz, CDCl 3 , 298 K) δ 7.61 (s, 1H), 7.44 (d, J = 8.3 Hz, 1H), 7.37 - 7.31 (m, 2H), 7.20 (t, J = 7.8 Hz, 1H), 3.93 (s, 3H).

[0111] 13 C NMR (150 MHz, C 2 D 2 Cl 4 , 298 K) δ 152.34, 152.05, 145.40, 140.65, 136.87, 132.44, 125.90, 125.23, 123.24, 121.43, 119.46, 110.41, 106.33, 104.33, 33.57.

[0112] HRMS(ESI) calculated for C 15 H 9 N 5 O 4 SBr + [M + H + 433.9553, found 433.9557.

[0113]

[0114] Example 14

[0115] Under an atmospheric environment, 50 mg of Compound B was dissolved in 2 mL of acetonitrile solution, then 9 μL of Compound m and 14 mg of sodium carbonate were added thereto, and then heated to 80 °C and reacted for 22 h. After the reaction was completed, it was concentrated under reduced pressure and purified by column chromatography to obtain 22 mg of a red solid with a yield of 45%.

[0116] 1 H NMR (600 MHz, DMSO - D 6 , 298 K) δ 11.79 (s, 1H), 7.28 (s, 1H), 6.62 (s, 1H), 6.35 - 6.33 (m, 1H).

[0117] 13 C NMR (150 MHz, DMSO - D 6 , 298 K) δ 152.38, 150.30, 144.41, 137.41, 125.42, 120.49, 119.52, 114.07, 110.79, 105.89, 39.52.

[0118] HRMS(ESI) calculated for C 10 H 3 N 5 O 4 SBr - [M - H + 367.9094, found 367.9100.

[0119]

[0120] Example 15

[0121] Under an atmospheric environment, 26 mg of Compound n was dissolved in 2 mL of acetonitrile solution, then 23 mg of Compound J and 14 mg of sodium carbonate were added thereto, and then heated to 80 °C and reacted for 6 h. After the reaction was completed, it was concentrated under reduced pressure and purified by column chromatography to obtain 16 mg of a dark blue solid with a yield of 36%.

[0122] 1 1H NMR (400 MHz, CDCl 3 , 298 K) δ 8.47 (d, J = 8.3 Hz, 1H), 7.74 (s, 2H), 7.51 (d, J = 8.1 Hz, 1H), 3.39 - 3.30 (m, 4H), 2.85 (t, J = 6.1 Hz, 4H), 2.02 (p, J = 6.0 Hz, 4H).

[0123] 13 13C NMR (150 MHz, C 2 D 2 Cl 4 , 298 K) δ 149.24, 146.32, 143.80, 138.91, 132.27, 130.37, 128.60, 121.71, 119.80, 119.42, 49.95, 27.71, 21.17.

[0124] HRMS (ESI) calculated for C 18 H 17 N 4 O 3 + [M + H + 337.1295, found 337.1297.

[0125]

[0126] Example 16

[0127] Under an atmospheric environment, 24 mg of compound o was dissolved in 2 mL of acetonitrile solution, then 23 mg of compound J and 14 mg of sodium carbonate were added thereto, and then heated to 80 °C and reacted for 18 h. After the reaction was completed, it was concentrated under reduced pressure and purified by column chromatography to obtain 23 mg of a yellow solid with a yield of 53%.

[0128] 1 1H NMR (600 MHz, CDCl 3 , 298 K) δ 7.90 (s, 2H), 3.35 - 3.31 (t, J = 6 Hz, 4H), 2.80 - 2.76 (t, J = 6 Hz, 4H), 1.97 (m, 4H).

[0129] 13 13C NMR (150 MHz, CDCl 3 , 298 K) δ 173.72, 170.70, 148.78, 129.70, 120.89, 117.69, 50.32, 27.77, 21.38.

[0130] HRMS(ESI) calculated for C 15 H 15 N 4 Cl 2 + [M + H + 321.0668, found 321.0668.

[0131]

[0132] Example 17

[0133] Under atmospheric conditions, 20 mg of compound p was dissolved in 2 mL of acetonitrile solution, then 23 mg of compound J and 14 mg of sodium carbonate were added thereto, and then heated to 80 °C and reacted for 2.5 h. After the reaction was completed, it was concentrated under reduced pressure and purified by column chromatography to obtain 10 mg of a purple solid with a yield of 10%.

[0134] 1 H NMR (600 MHz, CDCl 3 , 298 K) δ 7.96 (s, 2H), 3.33 - 3.30 (m, 4H), 2.82 (t, J = 6.3 Hz, 4H), 2.00 (dt, J = 12.8, 6.1 Hz, 4H).

[0135] 13 C NMR (150 MHz, CDCl 3 , 298 K) δ 165.39, 164.70, 147.25, 127.60, 121.53, 115.55, 50.17, 27.93, 21.54.

[0136] HRMS(ESI) calculated for C 14 H 15 N 5 Cl + [M + H + 288.1010, found 288.1013.

[0137]

[0138] Example 18

[0139] Under atmospheric conditions, 50 mg of compound B was dissolved in 2 mL of acetonitrile solution, then 45 mg of compound J and 42 mg of cesium carbonate were added, heated to 80 °C and stirred for reaction for 10 h. After the reaction was completed, it was concentrated under reduced pressure and purified by column chromatography to obtain 23 mg of a dark purple solid with a yield of 48%.

[0140] 1 H NMR (600 MHz, CDCl 3 , 298 K) δ 7.00 (s, 4H), 3.26 - 3.22 (t, J = 6.3 Hz, 8H), 2.79 (t, J = 6.3 Hz, 8H), 1.99 (p, J = 6.2 Hz, 8H).

[0141]

[0142] Example 19

[0143] Under atmospheric conditions, 50 mg of compound B was dissolved in 2 mL of acetonitrile solution, and then 64 mg of compound J1 and 42 mg of cesium carbonate were added. The mixture was heated to 80 °C and stirred for 12 h. After the reaction was completed, it was concentrated under reduced pressure and purified by column chromatography to obtain 30 mg of a dark purple solid with a yield of 32%.

[0144] 1 H NMR (600 MHz, CDCl 3 , 298 K) δ 7.27 (dd, J = 8.6, 2.4 Hz, 2H), 7.17 (d, J = 2.3 Hz, 2H), 6.63 (d, J = 8.7 Hz, 2H), 3.36 (t, J = 5.6 Hz, 4H), 3.28 (t, J = 7.6 Hz, 4H), 2.80 (t, J = 6.3 Hz, 4H), 1.98 (p, J = 6.1 Hz, 4H), 1.63 (p, J = 7.4 Hz, 4H), 1.34 - 1.27 (m, 26H).

[0145]

[0146] The following will use compound 1 obtained in Example 1 or compound 2 obtained in Example 18 as raw materials to synthesize near-infrared second-region fluorescent dyes based on benzobisthiadiazole, further illustrating the important application value of using the method of the present invention to prepare structures similar to compound 1 and compound 2.

[0147] Synthesis Example 1

[0148] 200 mg of compound 1, 122 mg of compound 3a and 25 mg of tetrakis(triphenylphosphine)palladium catalyst were added to a Schlenk flask. The flask was evacuated and backfilled with nitrogen three times to create a nitrogen-protected atmosphere. 5 mL of toluene and 2.5 mL of 2 M aqueous potassium carbonate solution were added. The reaction system was heated to 90 °C and stirred for 5 h. After cooling to room temperature, the organic phase was separated by liquid-liquid extraction, washed three times with saturated sodium chloride solution, dried over anhydrous sodium sulfate, and the solution was concentrated under reduced pressure. Purification by column chromatography gave a dark purple solid 3b. 100 mg of the dark purple solid compound 3b and 105 mg of iron powder were added to a Schlenk flask. The flask was evacuated and backfilled with nitrogen three times. 5 mL of glacial acetic acid was added. The reaction system was stirred at 80 °C for 4 h. After the reaction was completed, the reaction solution was poured into saturated sodium bicarbonate solution and filtered to obtain a brown solid. The crude product, 104 μL of N-phenylsulfonimide, and 118 μL of trimethylchlorosilane were dissolved in anhydrous pyridine. The reaction system was stirred at 80 °C for 24 h. After the reaction was completed, it was cooled to room temperature and the reaction system was poured into water and filtered to obtain a precipitate. The solid was purified by column chromatography to give 40 mg of a green solid (As1) with a yield of 42%.

[0149] 1 H NMR(600MHz,C 2 D 2 Cl 4 ,298K)δ8.23(d,J=8.6Hz,2H),7.80(s,2H),7.36(t,J=7.8Hz,4H),7.27(t,J=8.6Hz,6H),7.14(t,J=7.3Hz,2H),3.34-3.28(t,4H),2.92(t,J=6.0Hz,4H),2.07(p,J=5.9Hz,4H).

[0150] 13 C NMR(150MHz,CDCl 3 ,298K)δ153.18,152.64,148.03,147.55,144.02,132.63,131.06,129.52,129.21,125.41,123.62,122.56,122.15,121.23,117.90,50.22,28.09,22.05.

[0151] HRMS(ESI)calculated for C 36 H 29 N 6 S 2 + [M+H + 609.1889,found 609.1879.

[0152]

[0153] Synthesis Example 2

[0154] The reaction substrate 3a was replaced with compound 4a, and the remaining experimental conditions and operations were referred to Synthesis Example 1 to obtain 45 mg of green solid (As2), with a yield of 47%.

[0155] 1 H NMR (600 MHz, CD 2 Cl 2 , 298 K) δ 8.92 (d, J = 1.7 Hz, 1H), 8.31 (dd, J = 8.5, 1.7 Hz, 1H), 8.17 (d, J = 7.8 Hz, 1H), 7.78 (s, 2H), 7.64 (d, J = 8.5 Hz, 1H), 7.51 - 7.49 (m, 2H), 7.25 (ddd, J = 7.9, 5.0, 3.0 Hz, 1H), 4.47 (q, J = 7.2 Hz, 2H), 3.30 (t, J = 5.8 Hz, 4H), 2.90 (t, J = 6.4 Hz, 4H), 2.11 - 2.04 (m, 4H), 1.49 (t, J = 7.2 Hz, 3H).

[0156] 13 C NMR (100 MHz, CDCl 3 , 298 K) δ 153.58, 152.70, 143.98, 140.61, 140.22, 131.02, 129.53, 126.55, 125.97, 124.29, 123.59, 123.43, 122.69, 121.93, 121.28, 121.00, 119.61, 119.27, 108.77, 108.48, 50.26, 37.87, 28.14, 22.12, 14.10.

[0157] HRMS (ESI) calculated for C 32 H 27 N 6 S 2 + [M + H + 559.1733, found 559.1740.

[0158]

[0159] Synthesis Example 3

[0160] Replace the reaction substrate 3a with compound 5a, and refer to Synthesis Example 1 for the remaining experimental conditions and operations to obtain 58 mg of green solid (As3) with a yield of 62%.

[0161] 1 H NMR(600MHz,C 2 D 2 Cl 4 ,298K)δ8.22(d,J=8.8Hz,2H),7.80(s,2H),7.17(d,J=8.7Hz,2H),3.95(s,3H),3.32-3.29(m,4H),2.92(t,J=6.3Hz,4H),2.07(p,J=6.2Hz,4H).

[0162] 13 C NMR(100MHz,C 2 D 2 Cl 4 ,298K)δ159.40,152.90,152.15,143.69,132.96,131.16,127.98,122.09,121.92,120.85,117.34,113.74,55.45,49.90,27.80,21.76.

[0163] HRMS(ESI)calculated for C 25 H 22 N 5 OS 2 + [M+H + 472.1260,found 472.1255.

[0164]

[0165] Synthesis Example 4

[0166] Replace the reaction substrate 3a with compound 6a, and refer to Synthesis Example 1 for the remaining experimental conditions and operations to obtain 34 mg of green solid (As4) with a yield of 37%.

[0167] 1 H NMR(400MHz,CDCl 3 ,298K)δ8.17(d,J=7.5Hz,2H),7.83(s,2H),7.62(t,J=7.7Hz,2H),7.50(t,J=7.5Hz,1H),3.30(t,J=5.7Hz,4H),2.93(t,J=6.2Hz,4H),2.07(q,J=6.0,5.4Hz,4H).

[0168] 13 C NMR(100MHz,CDCl 3 , 298K) δ 153.48, 152.39, 144.19, 135.73, 131.63, 131.21, 128.53, 128.44, 123.27, 122.45, 121.26, 117.99, 50.23, 28.11, 22.03.

[0169] HRMS(ESI) calculated for C 24 H 20 N 5 S 2 + [M + H + 442.1154, found 442.1156.

[0170]

[0171] Synthesis Example 5

[0172] Using Compound 2 as the starting material, with the remaining experimental conditions and operations referring to Synthesis Example 1, 63 mg of a green solid (S0) was obtained, with a yield of 48%.

[0173] 1 H NMR(600MHz, CDCl 3 , 298K) δ 7.74(s, 4H), 3.29 - 3.25(t, J = 6.4Hz, 8H), 2.92(t, J = 6.4Hz, 8H), 2.05(p, J = 6.3Hz, 8H).

[0174] 13 C NMR(150MHz, CDCl 3 , 298K) δ 152.90, 143.61, 130.68, 122.87, 121.18, 119.91, 50.21, 28.07, 22.14.

[0175] HRMS(ESI) calculated for C 30 H 28 N 6 S 2 + [M + 536.1811, found 536.1813.

[0176]

[0177] Obviously, the above embodiments of the present invention are merely examples for clearly illustrating the present invention, rather than limitations on the implementation manners of the present invention. For those of ordinary skill in the art, other different forms of changes or modifications can be made based on the above description. It is impossible to list all the implementation manners here. Any obvious changes or modifications derived from the technical solutions of the present invention still fall within the protection scope of the present invention.

Claims

1. A method for constructing a carbon-carbon bond based on a carbon-halogen bond on an aromatic ring, characterized in that, it comprises the following steps: Dissolve an electron-deficient substrate containing a carbon-halogen bond in a solvent to obtain solution A; Add an electron-rich substrate and a basic compound to solution A to obtain solution B; Heat solution B under an atmospheric environment to complete the construction of the carbon-carbon bond through a coupling reaction; wherein, the electron-deficient substrate is selected from one of the general formula structures shown below: wherein X represents H, F, Cl, Br or NO 2 , and at least one X in the electron-deficient substrate represents F, Cl or Br; Y represents O, S, Se or CR 3 R 4 , where R 3 and R 4 may be the same or different and each independently represents H or an alkyl group having 1 to 3 carbon atoms; In the structure of formula I, the R 1 and R 2 may be the same or different and each independently represents H or NO 2 , and when R 1 and R 2 are both H, at least one X in the electron-deficient substrate represents NO 2 ; The electron-rich substrate is selected from nitrogen-containing aromatic hydrocarbons.

2. The method according to claim 1, characterized in that, the electron-deficient substrate is selected from one or more of the structures shown below:

3. The method according to claim 1, characterized in that, the electron-rich substrate is selected from one or more of the structures shown below:

4. The method according to claim 1, characterized in that, the reaction temperature of the coupling reaction is 25 - 100 °C, and the reaction time is 5 min - 96 h.

5. The method according to claim 1, characterized in that, the basic compound is selected from one or more of sodium carbonate, cesium carbonate, potassium carbonate, triethylamine, and N,N-diisopropylethylamine.

6. The method according to claim 1, characterized in that, the molar ratio of the electron-deficient substrate to the electron-rich substrate is 1:0.2 - 5.

7. The method according to claim 1, characterized in that, the solvent is selected from one or more of acetonitrile, dichloromethane, chloroform, and N,N-dimethylformamide.

8. The method according to claim 1, characterized in that, the concentration of the electron-deficient substrate in solution A is 6.5 mM to the saturation concentration.

9. The method according to claim 1, characterized in that, the concentration of the electron-rich substrate in solution B is 6.5 mM to the saturation concentration.

10. The method according to claim 1, characterized in that, the molar ratio of the electron-deficient substrate to the basic compound is 1:0.2 - 3.

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