Synthesis of benzofuran organic luminescent material intermediate

Abstract

The invention relates to the technical field of organic chemistry, and particularly discloses synthesis of a benzofuran organic light-emitting material intermediate.Compared with the prior art, reaction conditions are mild, the atom utilization rate is high, the amount of a noble metal catalyst used in the synthesis reaction is reduced, the path for synthesizing an organic light-emitting material is widened, and the synthesis cost is reduced. Compared with the prior art, different reaction initiators are used for synthesizing the organic light-emitting materials with the CAS numbers of 2701590-36-3, 278 6655-30-7 and 267 6940-58-0, the synthesis paths of a plurality of organic light-emitting materials are optimized, the production cost of unit organic substances is reduced, the selectivity of the synthesis paths is increased, and more substrates are provided for selection so as to control the synthesis cost.

Description

Technical Field

[0001] The invention relates to the technical field of organic chemistry, and specifically discloses the synthesis of a benzofuran-based organic luminescent material intermediate. Background Art

[0002] As an important intermediate, benzofuran compounds have been proposed in multiple patents for the synthesis of organic light-emitting materials, such as DE102021126547, WO2021150092 and CN 113121556 A. For example, in CN 113121556 A, it is used to synthesize the luminescent material A24, and the specific route is as follows:

[0003] For example, DE102021126547 is used to synthesize luminescent material 77, and the specific route is as follows:

[0004] CN 113121556 A requires a high dose of precious metal palladium catalyst, and DE102021126547 has complicated steps and requires multiple uses of chromatography to refine the crude product, resulting in a low final yield and driving up the preparation cost of a unit finished product. Summary of the invention

[0005] In view of the problems existing in the prior art, the first aspect of the present invention provides a method for synthesizing a benzofuran compound derivative represented by formula C, as follows: The compound of formula B is dissolved in an organic solvent, and then one of tricyclohexylphosphine tetrafluoroborate and tri-tert-butylphosphine tetrafluoroborate is added, and reacted with a base and a palladium salt under an inert gas atmosphere to obtain a compound of formula C.

[0006] .

[0007] In some specific embodiments of the first aspect of the present invention, the feeding amount of compound B per 1L of organic solvent is 251~302mmol, in some specific embodiments of the first aspect of the present invention, the feeding amount of compound B per 1L of organic solvent is 251mmol, in some specific embodiments of the first aspect of the present invention, the feeding amount of compound B per 1L of organic solvent is 260mmol, in some specific embodiments of the first aspect of the present invention, the feeding amount of compound B per 1L of organic solvent is 302mmol.

[0008] In some specific embodiments of the first aspect of the present invention, the amount of palladium acetate added per 1L of organic solvent is 4.76~6.05mmol, in some specific embodiments of the first aspect of the present invention, the amount of palladium acetate added per 1L of organic solvent is 5.05mmol, in some specific embodiments of the first aspect of the present invention, the amount of palladium acetate added per 1L of organic solvent is 5.60mmol, and in some specific embodiments of the first aspect of the present invention, the amount of palladium acetate added per 1L of organic solvent is 5.80mmol.

[0009] In some specific embodiments of the first aspect of the present invention, the feeding amount of one of tri-tert-butylphosphine tetrafluoroborate or tricyclohexylphosphine tetrafluoroborate per 1L of the organic solvent is 8.63~12.1mmol, in some specific embodiments of the first aspect of the present invention, the feeding amount of one of tri-tert-butylphosphine tetrafluoroborate or tricyclohexylphosphine tetrafluoroborate per 1L of the organic solvent is 9.0mmol, in some specific embodiments of the first aspect of the present invention, the feeding amount of one of tri-tert-butylphosphine tetrafluoroborate or tricyclohexylphosphine tetrafluoroborate per 1L of the organic solvent is 9.5mmol, in some specific embodiments of the first aspect of the present invention, the feeding amount of one of tri-tert-butylphosphine tetrafluoroborate or tricyclohexylphosphine tetrafluoroborate per 1L of the organic solvent is 11.0mmol.

[0010] In some specific embodiments of the first aspect of the present invention, the amount of the base added per 1L of the organic solvent is 503-604 mmol, in some specific embodiments of the first aspect of the present invention, the amount of the base added per 1L of the organic solvent is 530 mmol, in some specific embodiments of the first aspect of the present invention, the amount of the base added per 1L of the organic solvent is 545 mmol, in some specific embodiments of the first aspect of the present invention, the amount of the base added per 1L of the organic solvent is 570 mmol, and in some specific embodiments of the first aspect of the present invention, the amount of the base added per 1L of the organic solvent is 600 mmol.

[0011] In some specific embodiments of the first aspect of the present invention, the molar ratio of the compound B to palladium acetate is (25.1-27.2):(0.502-0.545); in some specific embodiments of the first aspect of the present invention, the molar ratio of the compound B to palladium acetate is (25-26):0.5.

[0012] In some specific embodiments of the first aspect of the present invention, the molar ratio of one of tri-tert-butylphosphine tetrafluoroborate or tricyclohexylphosphine tetrafluoroborate and the base is (0.8~1.2):(40~60); in some specific embodiments of the first aspect of the present invention, the molar ratio of one of tri-tert-butylphosphine tetrafluoroborate or tricyclohexylphosphine tetrafluoroborate and the base is (1.0~1.1):(50~55).

[0013] In some specific embodiments of the first aspect of the present invention, the base is selected from one or a mixture of potassium tert-butoxide, sodium tert-butoxide, cesium carbonate, and sodium carbonate.

[0014] In some specific embodiments of the first aspect of the present invention, the inert atmosphere is nitrogen atmosphere, argon atmosphere, or a mixture thereof.

[0015] In some specific embodiments of the first aspect of the present invention, the reaction temperature is 110-150°C, in some specific embodiments of the first aspect of the present invention, the reaction temperature is 120-140°C, and in some specific embodiments of the first aspect of the present invention, the reaction temperature is 130°C.

[0016] The second aspect of the present invention provides a method for synthesizing a benzofuran compound derivative represented by formula B, as follows: Compound A, compound Aa, cyclohexanediamine, cuprous iodide and potassium phosphate are added to an organic solvent and reacted under an inert gas atmosphere to obtain a compound of formula B; .

[0017] In some specific embodiments of the second aspect of the present invention, the molar amount of compound A per 1L of the organic solvent is 401~457mmol, in some specific embodiments of the second aspect of the present invention, the molar amount of compound A per 1L of the organic solvent is 410mmol, in some specific embodiments of the second aspect of the present invention, the molar amount of compound A per 1L of the organic solvent is 420mmol, in some specific embodiments of the second aspect of the present invention, the molar amount of compound A per 1L of the organic solvent is 430mmol, and in some specific embodiments of the second aspect of the present invention, the molar amount of compound A per 1L of the organic solvent is 440mmol.

[0018] In some specific embodiments of the second aspect of the present invention, the molar amount of compound Aa per 1L of the organic solvent is 604~686mmol, in some specific embodiments of the second aspect of the present invention, the molar amount of compound Aa per 1L of the organic solvent is 615mmol, in some specific embodiments of the second aspect of the present invention, the molar amount of compound Aa per 1L of the organic solvent is 630mmol, and in some specific embodiments of the second aspect of the present invention, the molar amount of compound Aa per 1L of the organic solvent is 650mmol.

[0019] In some specific embodiments of the second aspect of the present invention, the molar amount of cyclohexanediamine per 1L of the organic solvent is 16.1~18.3mmol, the molar amount of cyclohexanediamine per 1L of the organic solvent is 17.0mmol, the molar amount of cyclohexanediamine per 1L of the organic solvent is 17.5mmol, and the molar amount of cyclohexanediamine per 1L of the organic solvent is 18.0mmol.

[0020] In some specific embodiments of the second aspect of the present invention, the molar amount of cuprous iodide per 1L of the organic solvent is 8.19~9.9mmol, in some specific embodiments of the second aspect of the present invention, the molar amount of cuprous iodide per 1L of the organic solvent is 8.3mmol, and in some specific embodiments of the second aspect of the present invention, the molar amount of cuprous iodide per 1L of the organic solvent is 9.5mmol.

[0021] In some specific embodiments of the second aspect of the present invention, the molar amount of potassium phosphate per 1L of the organic solvent is 860~914mmol, in some specific embodiments of the second aspect of the present invention, the molar amount of potassium phosphate per 1L of the organic solvent is 890mmol, and in some specific embodiments of the second aspect of the present invention, the molar amount of potassium phosphate per 1L of the organic solvent is 910mmol.

[0022] In some specific embodiments of the second aspect of the present invention, the molar ratio of compound A to compound Aa is (80.1~96.1):(120.8~144.2); in some specific embodiments of the second aspect of the present invention, the molar ratio of compound A to compound Aa is 90:130.

[0023] In some specific embodiments of the second aspect of the present invention, the molar ratio of cyclohexanediamine to cuprous iodide is (3.22-3.84):(1.61-1.98); in some specific embodiments of the second aspect of the present invention, the molar ratio of cyclohexanediamine to cuprous iodide is 3.5:1.7.

[0024] In some specific embodiments of the second aspect of the present invention, the molar ratio of compound A to potassium phosphate is (80.1~96.1):(172~192); in some specific embodiments of the second aspect of the present invention, the molar ratio of compound A to potassium phosphate is 90:180.

[0025] In some specific embodiments of the second aspect of the present invention, the organic solvent is selected from DMF, acetonitrile, alcohols, dichloromethane or a mixture thereof.

[0026] In some specific embodiments of the second aspect of the present invention, the inert atmosphere is argon, nitrogen, or a mixture thereof.

[0027] In some specific embodiments of the second aspect of the present invention, the reaction temperature is 100-140°C, in some specific embodiments of the second aspect of the present invention, the reaction temperature is 100°C, in some specific embodiments of the second aspect of the present invention, the reaction temperature is 120°C, and in some specific embodiments of the second aspect of the present invention, the reaction temperature is 140°C.

[0028] The third aspect of the present invention is the use of a compound represented by formula C in the preparation of an organic light-emitting material.

[0029] The third aspect proposes the use of a compound represented by formula II in the preparation of an organic light-emitting material.

[0030] The reagents used in the present invention are purchased from the open market, such as McLean reagent, Sinopharm chemical reagent, Xilong chemical reagent, and Sigma chemical reagent. The purity level of the reagents put into the reaction system of the synthesis step is AR or above, and the purity of the reagents used in the analysis and test is GR or HPLC grade or above, and has not been further purified.

[0031] “w / w” stands for mass fraction, and “ND” stands for below detection limit.

[0032] In the present invention, "room temperature" refers to a temperature from about 10°C to about 40°C. In some embodiments, "room temperature" refers to a temperature from about 20°C to about 30°C; in other embodiments, "room temperature" refers to 22.5°C, 25°C, 27.5°C, etc.

[0033] The yield formula of the present invention is: Unless otherwise specified, the experimental operations of the present invention are all performed under standard atmospheric pressure.

[0034] Advantages of the present invention: The invention relates to the technical field of organic chemistry, and specifically discloses a synthesis of a benzofuran-based organic luminescent material intermediate. Compared with the prior art, the invention has relatively mild reaction conditions, high atom utilization rate, reduced amount of noble metal catalysts used in a synthesis reaction, and broadened the path for synthesizing organic luminescent materials. Compared with the prior art, different reaction starting materials are used to synthesize organic luminescent materials with CAS numbers of 2701590-36-3, 2786655-30-7, and 2676940-58-0, thereby optimizing the synthesis paths of multiple organic luminescent materials, reducing preparation costs, and broadening selectivity. BRIEF DESCRIPTION OF THE DRAWINGS

[0035] Figure 1 14 shows the hydrogen spectrum NMR data of compound C of the present invention; DETAILED DESCRIPTION

[0036] The following will be combined with the drawings in the embodiments of the present application to clearly and completely describe the technical solutions in the embodiments of the present application. Obviously, the described embodiments are only part of the embodiments of the present application, not all of the embodiments. Based on the embodiments in the present application, all other embodiments obtained by ordinary technicians in this field based on the present application belong to the scope of protection of the present application.

[0037] The synthetic route of the present invention is summarized as follows:

[0038] S1: Add compound A and compound Aa to an organic solvent, then add cyclohexanediamine, cuprous iodide and potassium phosphate, replace with inert gas, stir and heat, use TLC to observe the reaction degree of the raw materials, and return to room temperature.

[0039] Water was added to the reaction solution, and then extracted with ethyl acetate. The organic phase was washed with water three times, dried over anhydrous sodium sulfate, and concentrated on a silica gel column to obtain a crude product, which was then crystallized with ethyl acetate and petroleum ether to obtain compound B.

[0040] S2: Compound B is dissolved in an organic solvent, palladium acetate, tri-tert-butylphosphine tetrafluoroborate and sodium tert-butoxide are added, the inert gas is replaced, the temperature is raised by stirring, and the reaction is refluxed. The TLC plate shows that the reaction is complete, water is added to the reaction solution, and then extracted with ethyl acetate. The organic phase is then washed with water three times, dried with anhydrous sodium sulfate, and the organic phase is concentrated by silica gel column to obtain a crude product, which is then crystallized with toluene to obtain compound C.

[0041] The following describes the process through specific implementation: Embodiment 1:

[0042] Compound A (91.5 mmol) and compound Aa (137.2 mmol) were added to DMF (200 mL), and then cyclohexanediamine (3.66 mmol), cuprous iodide (1.83 mmol) and potassium phosphate (180 mmol) were added, and nitrogen was replaced 3 times. Stir and heat to 120°C. TLC spot plate showed that the raw materials were basically reacted and returned to room temperature. Water was added to the reaction solution, and then extracted with ethyl acetate. The organic phase was washed with water three times, dried over anhydrous sodium sulfate, and the organic phase was concentrated by brushing with a silica gel column to obtain a crude product, which was then crystallized with ethyl acetate and petroleum ether to obtain compound B (81.3% yield).

[0043]

[0044] Compound B (26.8 mmol) was dissolved in xylene (100 mL), palladium acetate (0.505 mmol), tri-tert-butylphosphine tetrafluoroborate (1.01 mmol) and sodium tert-butoxide (53.6 mmol) were added, and the atmosphere was replaced with nitrogen three times. The mixture was stirred and heated to reflux at 130°C for reaction. TLC showed that the reaction was complete, and water was added to the reaction solution, and then extracted with ethyl acetate. The organic phase was washed with water three times, dried over anhydrous sodium sulfate, and concentrated on a silica gel column to obtain a crude product, which was then crystallized from toluene to obtain compound C (yield 85.1%).

[0045] 1 H NMR (400 MHz, Chloroform-d) δ 8.42 (dd, J = 7.8, 1.3 Hz, 1H), 8.29 (dd, J = 7.3, 1.3 Hz, 1H), 7.74 - 7.69 (m, 1H), 7.66 - 7.61 (m, 1H), 7.59 (s,1H), 7.54-7.51 (m, 2H), 7.48-7.42 (m, 2H).

[0046] Embodiment 2: Compound A (80.5 mmol) and compound Aa (120.8 mmol) were added to DMF (200 mL), and then cyclohexanediamine (3.22 mmol), cuprous iodide (1.61 mmol) and potassium phosphate (172 mmol) were added, and nitrogen was replaced three times. Stir and heat to 130°C. TLC spot plate showed that the raw materials were basically reacted and returned to room temperature. Water was added to the reaction solution, and then extracted with ethyl acetate. The organic phase was washed with water three times, dried over anhydrous sodium sulfate, and the organic phase was concentrated by brushing with a silica gel column to obtain a crude product, which was then crystallized with ethyl acetate and petroleum ether to obtain compound B (75.2% yield).

[0047] Compound B (27.2 mmol) was dissolved in xylene (90 mL), palladium acetate (0.545 mmol), tri-tert-butylphosphine tetrafluoroborate (1.09 mmol) and potassium tert-butoxide (54.4 mmol) were added, and the atmosphere was replaced with nitrogen three times. The mixture was stirred and heated to reflux at 140°C for reaction. TLC showed that the reaction was complete, and water was added to the reaction solution, and then extracted with ethyl acetate. The organic phase was washed with water three times, dried over anhydrous sodium sulfate, and concentrated by brushing with a silica gel column to obtain a crude product, which was then crystallized from toluene to obtain compound C (yield 77.3%).

[0048] 1 H NMR (400 MHz, Chloroform-d) δ 8.42 (dd, J = 7.8, 1.3 Hz, 1H), 8.29 (dd, J = 7.3, 1.3 Hz, 1H), 7.74 - 7.69 (m, 1H), 7.66 - 7.61 (m, 1H), 7.59 (s,1H), 7.54-7.51 (m, 2H), 7.48-7.42 (m, 2H).

[0049] Embodiment 3: Compound A (96.1 mmol) and compound Aa (144.2 mmol) were added to DMF (210 mL), and then cyclohexanediamine (3.84 mmol), cuprous iodide (1.92 mmol) and potassium phosphate (172 mmol) were added, and nitrogen was replaced 3 times. Stir and heat to 110°C. TLC spot plate showed that the raw materials were basically reacted and returned to room temperature. Water was added to the reaction solution, and then extracted with ethyl acetate. The organic phase was washed with water three times, dried over anhydrous sodium sulfate, and the organic phase was concentrated by brushing with a silica gel column to obtain a crude product, which was then crystallized with ethyl acetate and petroleum ether to obtain compound B (76.9% yield).

[0050] Compound B (26.2 mmol) was dissolved in xylene (110 mL), palladium acetate (0.524 mmol), tri-tert-butylphosphine tetrafluoroborate (0.95 mmol) and sodium tert-butoxide (55.4 mmol) were added, and the atmosphere was replaced with nitrogen three times. The mixture was stirred and heated to reflux at 120°C for reaction. TLC showed that the reaction was complete, and water was added to the reaction solution, and then extracted with ethyl acetate. The organic phase was washed with water three times, dried over anhydrous sodium sulfate, and concentrated by brushing with a silica gel column to obtain a crude product, which was then crystallized from toluene to obtain compound C (yield 81.5%).

[0051] 1H NMR (400 MHz, Chloroform-d) δ 8.42 (dd, J = 7.8, 1.3 Hz, 1H), 8.29 (dd, J = 7.3, 1.3 Hz, 1H), 7.74 - 7.69 (m, 1H), 7.66 - 7.61 (m, 1H), 7.59 (s,1H), 7.54-7.51 (m, 2H), 7.48-7.42 (m, 2H).

[0052] Embodiment 4: Compound A (80.1 mmol) and compound Aa (137.0 mmol) were added to NMP (200 mL), and then cyclohexanediamine (3.27 mmol), cuprous iodide (1.98 mmol) and potassium phosphate (172 mmol) were added, and nitrogen was replaced three times. Stir and heat to 120°C. TLC spot plate showed that the raw materials were basically reacted and returned to room temperature. Water was added to the reaction solution, and then extracted with ethyl acetate. The organic phase was washed with water three times, dried over anhydrous sodium sulfate, and the organic phase was concentrated by brushing with a silica gel column to obtain a crude product, which was then crystallized with ethyl acetate and petroleum ether to obtain compound B (82.9% yield).

[0053] Compound B (25.1 mmol) was dissolved in xylene (100 mL), palladium acetate (0.502 mmol), tricyclohexylphosphine tetrafluoroborate (1.12 mmol) and sodium tert-butoxide (50.2 mmol) were added, and the atmosphere was replaced with nitrogen three times. The mixture was stirred and heated to reflux at 130°C for reaction. TLC showed that the reaction was complete, and water was added to the reaction solution, and then extracted with ethyl acetate. The organic phase was washed with water three times, dried over anhydrous sodium sulfate, and concentrated on a silica gel column to obtain a crude product, which was then crystallized from toluene to obtain compound C (yield 71.7%).

[0054] 1 H NMR (400 MHz, Chloroform-d) δ 8.42 (dd, J = 7.8, 1.3 Hz, 1H), 8.29 (dd, J = 7.3, 1.3 Hz, 1H), 7.74 - 7.69 (m, 1H), 7.66 - 7.61 (m, 1H), 7.59 (s,1H), 7.54-7.51 (m, 2H), 7.48-7.42 (m, 2H).

[0055] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims

1. A method for synthesizing a benzofuran compound derivative represented by formula C, as follows: The compound of formula B is dissolved in an organic solvent, and then one of tricyclohexylphosphine tetrafluoroborate and tri-tert-butylphosphine tetrafluoroborate is added, and reacted with a base and a palladium salt under an inert gas atmosphere to obtain a compound of formula C; 。 2. The method for synthesizing the compound of formula C according to claim 1, characterized in that: The amount of compound B added per 1L of organic solvent is 251~302mmol, preferably 270mmol, and / or the amount of palladium acetate added per 1L of organic solvent is 4.76~6.05mmol, preferably 5.05mmol, and / or the amount of one of tri-tert-butylphosphine tetrafluoroborate or tricyclohexylphosphine tetrafluoroborate added per 1L of the organic solvent is 8.63~12.1mmol, preferably 10.1mmol, and / or the amount of sodium tert-butoxide added per 1L of the organic solvent is 503~604mmol, preferably 536mmol.

3. A method for synthesizing a compound of formula C according to any one of claims 1 or 2, characterized in that: The molar ratio of the compound B to the palladium salt is (25.1-27.2):(0.502-0.545), and / or the molar ratio of one of the tricyclohexylphosphine tetrafluoroborate or tri-tert-butylphosphine tetrafluoroborate to the base is (0.95-1.12):(50.2-55.4).

4. A method for synthesizing a compound of formula C according to any one of claims 1 to 3, characterized in that: The palladium salt is palladium acetate, and / or the base is selected from one or a mixture of potassium tert-butoxide, sodium tert-butoxide, cesium carbonate, and sodium carbonate, and / or the inert atmosphere is one or a mixture of nitrogen atmosphere and argon atmosphere, and / or the reaction temperature is 130-140° C., preferably 130° C.

5. A method for synthesizing a benzofuran compound derivative represented by formula B, as follows: Compound A, compound Aa, cyclohexanediamine, cuprous iodide and potassium phosphate are added to an organic solvent and reacted under an inert gas atmosphere to obtain a compound of formula B; 。 6. The method for synthesizing the compound of formula B according to claim 5, characterized in that: The molar amount of compound A per 1L of the organic solvent is 401-457 mmol, preferably 457 mmol, and / or the molar amount of compound Aa per 1L of the organic solvent is 604-686 mmol, preferably 686 mmol.

7. The method for synthesizing the compound of formula B according to claim 6, characterized in that: The molar amount of cyclohexanediamine per 1L of the organic solvent is 16.1-18.3 mmol, preferably 18.3 mmol, and / or the molar amount of cuprous iodide per 1L of the organic solvent is 8.19-9.9 mmol, preferably 9.15 mmol, and / or the molar amount of potassium phosphate per 1L of the organic solvent is 860-914 mmol, preferably 900 mmol.

8. A method for synthesizing a compound of formula B according to any one of claims 5 or 6, characterized in that: The molar ratio of compound A to compound Aa is (80.1-96.1):(120.8-144.2), and / or the molar ratio of cyclohexanediamine to cuprous iodide is (3.22-3.84):(1.61-1.98), and / or the molar ratio of compound A to potassium phosphate is (80.1-96.1):(172-192).

9. A method for synthesizing a compound of formula B according to any one of claims 5 to 7, characterized in that: The organic solvent is selected from one of DMF, acetonitrile, NMP, alcohols, and dichloromethane, or a mixture thereof; the inert atmosphere is one of argon and nitrogen, or a mixture thereof; and / or the reaction temperature is 100-140° C., preferably 120° C.

10. Use of a compound represented by formula C in the preparation of an organic light-emitting material.

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