A method for synthesizing [60]fullerene-allylbenzofuran derivatives catalyzed by palladium

Abstract

The invention discloses a method for synthesizing [60]fullerene-allylbenzofuran derivatives by palladium catalysis, and belongs to the technical field of synthesis of fullerene derivatives. The technical scheme of the invention is as follows: 1,2-bis(diphenylphosphino)benzene is used as a ligand, and allyloxy aryl iodide and [60]fullerene are migrated under the catalytic action of Pd2(dba)3 to obtain the target product [60]fullerene-allylbenzofuran derivative. The invention has high chemical selectivity and regioselectivity, a wide range of substrates, mild reaction conditions, a simple production process, and a high yield.

Description

Technical Field

[0001] The present invention belongs to the technical field of synthesis of fullerene derivatives, and in particular relates to a method for synthesizing

[60] fullerene-allyl benzofuran derivatives by palladium catalysis. Background Art

[0002] In the past 30 years, the chemical functionalization of fullerenes has received special attention. The functionalization of fullerenes provides many opportunities for the development of functional fullerene materials, which can not only improve the solubility of fullerenes, but also change their electronic structure and optoelectronic properties. Therefore, exploring new fullerene modification methods and constructing fullerenes with different functional groups are crucial for the development of fullerene derivatives in different fields. Summary of the invention

[0003] The technical problem solved by the present invention is to provide a method for synthesizing

[60] fullerene-allylbenzofuran derivatives by palladium catalysis. The method uses 1,2-bis(diphenylphosphino)benzene (DPPBz) as a ligand, and allyloxy aromatic iodide and

[60] fullerene migrate under the catalytic action of Pd2(dba)3 to obtain the target product

[60] fullerene-allylbenzofuran derivative. The method has high chemical selectivity and regioselectivity, a wide substrate range, mild reaction conditions, a simple production process and a high yield.

[0004] The present invention adopts the following technical scheme to solve the above technical problems. A method for synthesizing

[60] fullerene-allylbenzofuran derivatives by palladium catalysis is characterized in that the specific process is: using 1,2-bis(diphenylphosphino)benzene as a ligand, allyloxy aromatic iodide and

[60] fullerene migrate under the catalytic action of Pd2(dba)3 to obtain the target product

[60] fullerene-allylbenzofuran derivatives. The reaction equation in the synthesis process is:

[0005]

[0006] Among them, the allyl oxide aryl iodide is

[0007] The corresponding

[60] fullerene-allylbenzofuran derivative is

[0008] Further defined, the method for the palladium-catalyzed synthesis of

[60] fullerene-allylbenzofuran derivatives is characterized by the specific steps of: placing

[60] fullerene, allyloxy aromatic iodide, Pd2(dba)3, 1,2-bis(diphenylphosphino)benzene and Cs2CO3 in a dry Shrek tube, dissolving them in anhydrous ODCB and 1,4-dioxane solvents by ultrasonic treatment, heating and stirring the sealed mixture at 130°C for reaction, cooling to room temperature after the reaction stops, filtering out insoluble matter, and removing the solvent under reduced pressure, first using CS2 as an eluent to collect unreacted

[60] fullerene, and then switching the eluent to CS2 / DCM to finally obtain the target product

[60] fullerene-allylbenzofuran derivatives.

[0009] It is further defined that the molar ratio of the

[60] fullerene, allyloxy aromatic iodide, Pd2(dba)3, 1,2-bis(diphenylphosphino)benzene and Cs2CO3 is 1:5:0.1:0.2:2.

[0010] The present invention has the following advantages and beneficial effects: the present invention has high chemical selectivity and regional selectivity, a wide range of substrates, mild reaction conditions, a simple production process and a high yield. DETAILED DESCRIPTION

[0011] The above contents of the present invention are further described in detail below through examples, but this should not be understood as the scope of the above subject matter of the present invention being limited to the following examples, and all technologies implemented based on the above contents of the present invention belong to the scope of the present invention.

[0012]

[0013] Example 1

[0014] Preparation of

[60] fullerene-allylbenzofuran derivative 2a:

[0015]

[0016] Reaction steps:

[0017] Accurately weigh

[60] fullerene (0.05 mmol), allyloxy aryl iodide 1a (0.25mmol), 1,2-bis(diphenylphosphino)benzene (0.01mmol), Cs2CO3 (0.1mmol) and Pd2(dba)3 (0.005mmol) were placed in a 15mL dry Shrek tube and dissolved in anhydrous ODCB and 1,4-dioxane solvent by ultrasonic treatment. The sealed mixture was heated and stirred in an oil bath at 130°C for reaction. After the reaction stopped, it was cooled to room temperature, the insoluble matter was filtered out, and the solvent was removed under reduced pressure. CS2 was used as the eluent to collect the unreacted

[60] fullerene, and then the eluent was switched to CS2 / DCM to finally obtain the target product

[60] fullerene-allylbenzofuran derivative 2a, and the relative yield of product 2a was 46%.

[0018] 2a: 1 H NMR (600MHz, CDCl3 / CS2) δ8.00(d,J=8.4Hz,2H),7.72(d,J=7.2Hz,1H),7.70(d,J=8.4Hz,2H),7.30(d,J=7.8Hz, 1H),7.14(t,J=7.8Hz,1H),5.72(s,1H),5.46(s,1H),4.33(q,J=7.2Hz,2H),4.24(s,2H),1.38(t,J=7.2Hz,3H); 13 C NMR(150MHz,CDCl3 / CS2with Cr(acac)3as relaxation reagent)δ166.0,155.4,150.6,148.1,147.3,146.25,146.17,146.1,146.0,145.9,145.45 ,145.40,145.2,145.12,145.09,145.07,145.00,144.96,144.8,144.4,144.3,142.8,142.6 5,142.62,142.25,142.21,142.1,141.70,141.69,140.7,139.7,137.5,135.6,130.9,129.6 ,129.5,126.2,126.1,123.7,123.5,122.6,116.5,102.6,71.3,60.8,35.4,14.4; FT-IRν / cm -1 1712,1607,1450,1274,1107,1015,946,923,861,782,526; UV-vis(CHCl3)λ max / nm 256,316,427,691; MALDI-TOFMS m / z calcd for C 78 H16 O3[M] - 1000.1105, found 1000.1112.

[0019] Example 2

[0020] Preparation of

[60] fullerene-allylbenzofuran derivative 2b:

[0021]

[0022] Reaction steps:

[0023] Accurately weigh

[60] fullerene (0.05 mmol), allyloxy aryl iodide 1b (0.25mmol), 1,2-bis(diphenylphosphino)benzene (0.01mmol), Cs2CO3 (0.1mmol) and Pd2(dba)3 (0.005mmol) were placed in a 15mL dry Shrek tube. After being dissolved in anhydrous ODCB and 1,4-dioxane solvent by ultrasonic treatment, the sealed mixture was heated and stirred in an oil bath at 130°C for reaction. After the reaction stopped, it was cooled to room temperature, the insoluble matter was filtered off, and the solvent was removed under reduced pressure. CS2 was used as an eluent to collect the unreacted

[60] fullerene, and then the eluent was switched to CS2 / DCM to finally obtain the target product

[60] fullerene-allylbenzofuran derivative 2b, and the relative yield of product 2b was 33%.

[0024] 2b: 1 H NMR (600MHz, CDCl3 / CS2) δ8.35(s,1H),7.96(t,J=7.8Hz,1H),7.85(d,J=7.8Hz,1H),7.76(d,J=7.2Hz,1H),7.43(t,J=7.8Hz,1H), 7.37(d,J=7.8Hz,1H),7.19(d,J=7.8Hz,1H),5.69(s,1H),5.44(s,1H),4.37(q,J=7.2Hz,2H),4.28,(s,1H),1.39(t,J=7.2Hz,3H); 13C NMR(150MHz,CDCl3 / CS2 with Cr(acac)3as relaxation reagent)δ166.5,155.5,150.8,148.2,147.4,146.4,146.25,146.18,146.1,146.0,145.6,14 5.3,145.22,145.19,145.14,145.09,144.5,144.4,142.9,142.73,142.70,142.67,142.33,1 42.29,142.2,141.78,141.76,141.0,140.8,139.8,137.6,135.8,131.1,130.8,130.6,128.7 ,128.4,127.6,126.3,123.74,123.71,122.6,115.7,102.7,71.5,61.0,35.6,14.4; FT-IRν / cm -1 1712,1451,1240,1102,1016,905,746,526; UV-vis(CHCl3)λ max / nm 255,316,427,690; MALDI-TOF MS m / z calcd for C 78 H 16 O3[M] - 1000.1105, found 1000.1109.

[0025] Example 3

[0026]

[60] Fullerene-allylbenzofuran derivative 2c:

[0027]

[0028] Reaction steps:

[0029] Accurately weigh

[60] fullerene (0.05 mmol), allyloxyaryl iodide 1c (0.25mmol), 1,2-bis(diphenylphosphino)benzene (0.01mmol), Cs2CO3 (0.1mmol) and Pd2(dba)3 (0.005mmol) were placed in a 15mL dry Shrek tube and dissolved in anhydrous ODCB and 1,4-dioxane solvent by ultrasonic treatment. The sealed mixture was heated and stirred in an oil bath at 130°C for reaction. After the reaction stopped, it was cooled to room temperature, the insoluble matter was filtered out, and the solvent was removed under reduced pressure. CS2 was used as the eluent to collect the unreacted

[60] fullerene, and then the eluent was switched to CS2 / DCM to finally obtain the target product

[60] fullerene-allylbenzofuran derivative 2c. The relative yield of product 2c was 39%.

[0030] 2c: 1 H NMR (600MHz, CDCl3 / CS2) δ7.77(d,J=8.4Hz,2H),7.76(d,J=6.6Hz,1H),7.64(d,J=8.4Hz, 2H),7.31(d,J=7.8Hz,1H),7.17(t,J=7.8Hz,1H),5.75(s,1H),5.54(s,1H),4.24(s,1H); 13 C NMR(150MHz,DMSO-d6 / CS2 with Cr(acac)3as relaxationreagent)δ154.4,149.5,147.1,146.3,145.3,145.2,145.1,145.0,144.9,1 44.4,144.3,144.2,144.13,144.08,144.0,143.9,143.5,143.4,143.3,141.9,141.69, 141.66,141.3,141.2,141.1,140.75,140.70,139.8,138.8,136.4,134.6,131.2,130.2 ,126.2,125.0,123.0,122.2,122.1,116.9,116.7,110.9,101.5,70.3,34.3; FT-IRν / cm -1 2223,1709,1510,1448,1255,1103,1013,945,920,846,742,526; UV-vis(CHCl3)λ max / nm 255,316,427,691; MALDI-TOF MS m / zcalcd for C 76 H 11 NO[M] - 953.0846,found953.0853.

[0031] Example 4

[0032]

[60] Fullerene-allylbenzofuran derivative 2d:

[0033]

[0034] Reaction steps:

[0035] Accurately weigh

[60] fullerene (0.05 mmol), allyloxy aryl iodide 1d (0.25mmol), 1,2-bis(diphenylphosphino)benzene (0.01mmol), Cs2CO3 (0.1mmol) and Pd2(dba)3 (0.005mmol) were placed in a 15mL dry Shrek tube and dissolved in anhydrous ODCB and 1,4-dioxane solvent by ultrasonic treatment. The sealed mixture was heated and stirred in an oil bath at 130°C for reaction. After the reaction stopped, it was cooled to room temperature, the insoluble matter was filtered out, and the solvent was removed under reduced pressure. CS2 was used as the eluent to collect the unreacted

[60] fullerene, and then the eluent was switched to CS2 / DCM to finally obtain the target product

[60] fullerene-allylbenzofuran derivative 2d, and the relative yield of product 2d was 35%.

[0036] 2d: 1 H NMR (600MHz, CD2Cl2 / CS2) δ7.76(s,4H),7.73(m,3H),7.53(t,J=7.8Hz,1H),7.44(t,J=7.2H z,2H),7.34(d,J=7.2Hz,1H),7.16(t,J=7.8Hz,1H),5.78(s,1H),5.49(s,1H),4.27(s,2H); 13C NMR(150MHz,CDCl3 / CS2 with Cr(acac)3as relaxationreagent)δ192.5,154.4,149.6,147.1,146.3,145.3,145.2,145.1,145.0,144 .9,144.4,144.2,144.1,144.0,143.9,143.4,143.3,143.0,141.9,141,69,141.66,141.29 ,141.25,141.1,140.8,140.7,139.8,138.8,136.6,136.4,135.5,134.6,131.0,130.2,12 9.3,128.9,127.3,125.3,124.9,122.9,122.6,122.1,115.9,101.5,70.4,34.4; FT-IRν / cm - 1 1657,1601,1451,1315,1277,1104,916,859,707,527; UV-vis(CHCl3)λ max / nm 255,316,425,690; MALDI-TOF MS m / zcalcd for C 82 H 16 O2[M] - 1032.1156, found 1032.1161.

[0037] Example 5

[0038]

[60] Fullerene-allylbenzofuran derivative 2e:

[0039]

[0040] Reaction steps:

[0041] Accurately weigh

[60] fullerene (0.05 mmol), allyloxy aryl iodide 1e (0.25mmol), 1,2-bis(diphenylphosphino)benzene (0.01mmol), Cs2CO3 (0.1mmol) and Pd2(dba)3 (0.005mmol) were placed in a 15mL dry Shrek tube and dissolved in anhydrous ODCB and 1,4-dioxane solvent by ultrasonic treatment. The sealed mixture was heated and stirred in an oil bath at 130°C for reaction. After the reaction stopped, it was cooled to room temperature, the insoluble matter was filtered out, and the solvent was removed under reduced pressure. CS2 was used as the eluent to collect the unreacted

[60] fullerene, and then the eluent was switched to CS2 / DCM to finally obtain the target product

[60] fullerene-allylbenzofuran derivative 2e, and the relative yield of product 2e was 37%.

[0042] 2e: 1 H NMR (600MHz, CDCl3 / CS2) δ7.71(d,J=8.4Hz,2H),7.70(d,J=7.8Hz,1H),7.54(d,J=8.4Hz ,2H),7.27(d,J=7.8Hz,1H),7.11(t,J=7.2Hz,1H),5.68(s,1H),5.44(s,1H),4.2(s,2H); 13 C NMR(150MHz,CDCl3 / CS2 with Cr(acac)3as relaxation reagent)δ155.3,150.4,147.9,147.2,146.1,146.0,145.9,145.8,145.7,145.3,14 5.2,145.04,144.97,144.9,144.8,144.7,144.5,144.2,144.1,143.8,142.7,142.50 ,142.47,142.46,142.09,142.06,141.9,141.6,141.5,140.6,139.6,137.3,135.5,1 30.7,126.5,126.0,125.1,123.6,123.2,122.6,116.6,102.5,71.2,35.2; FT-IRν / cm -1 1616,1512,1452,1429,1325,1166,1124,1067,1015,846,743,527; UV-vis(CHCl3)λ max / nm 255,314,426,692.MALDI-TOF MS m / zcalcd for C 76 H 11 F3O[M] - 996.0767, found 996.0775.

[0043] Example 6

[0044]

[60] Fullerene-allylbenzofuran derivative 2f:

[0045]

[0046] Reaction steps:

[0047] Accurately weigh

[60] fullerene (0.05 mmol), allyloxy aryl iodide 1f (0.25mmol), 1,2-bis(diphenylphosphino)benzene (0.01mmol), Cs2CO3 (0.1mmol) and Pd2(dba)3 (0.0075mmol) were placed in a 15mL dry Shrek tube and dissolved in anhydrous ODCB and 1,4-dioxane solvent by ultrasonic treatment. The sealed mixture was heated and stirred in an oil bath at 130°C for reaction. After the reaction stopped, it was cooled to room temperature, the insoluble matter was filtered out, and the solvent was removed under reduced pressure. CS2 was used as the eluent to collect the unreacted

[60] fullerene, and then the eluent was switched to CS2 / DCM to finally obtain the target product

[60] fullerene-allylbenzofuran derivative 2f, and the relative yield of product 2f was 27%.

[0048] 2f: 1 H NMR (600MHz, CDCl3 / CS2) δ8.03(d,J=8.4Hz,2H),7.85(s,2H),7.70(d,J=8.4Hz,2H),5.50( s,1H),5.16(s,1H),4.60(s,2H),4.35(q,J=7.2Hz,2H),3.92(s,3H),1.38(t,J=7.2Hz,3H); 1 H NMR (600MHz, C6D6) δ8.18(d,J=8.4Hz,2H),7.94(d,J=7.8Hz,1H),7.61(d,J=8.4Hz,2H),7.54(d,J=7.8H z,1H),5.45(s,1H),5.35(s,1H),4.79(s,2H),4.13(q,J=7.2Hz,2H),3.55(s,3H),1.03(t,J=7.2Hz,3H); 13C NMR(150MHz,CDCl3 / CS2with Cr(acac)3as relaxation reagent)δ167.4,166.5,157.1,150.3,148.4,147.62,147.57,146.51,146.49,146.45,146.39, 146.3,146.2,145.6,145.5,145.4,145.3,145.2,145.12,145.08,144.6,144.5,143.1,142.91,1 42.89,142.7,142.49,142.45,142.3,141.95,141.86,141.0,140.0,137.6,136.1,132.7,130.2, 129.7,129.5,126.6,125.5,125.2,123.5,114.8,103.0,71.4,61.0,52.4,32.9,14.5; FT-IRν / cm -1 1722,1433,1275,1107,1019,673,527; UV-vis(CHCl3)λ max / nm255,315,427,691; MALDI-TOF MS m / zcalcdfor C 80 H 18 O5[M] - 1058.1160, found 1058.1167.

[0049] The above embodiments describe the basic principles, main features and advantages of the present invention. Those skilled in the art should understand that the present invention is not limited to the above embodiments. The above embodiments and descriptions are only for illustrating the principles of the present invention. Without departing from the scope of the principles of the present invention, the present invention may have various changes and improvements, and these changes and improvements all fall within the scope of protection of the present invention.

Claims

1. A method for synthesizing [60]fullerene-allylbenzofuran derivatives catalyzed by palladium, characterized in that The specific process is as follows: [60]fullerene, allyloxy aromatic iodide, catalyst Pd2(dba)3, ligand 1,2-bis(diphenylphosphino)benzene and Cs2CO3 are placed in a dry Shrek tube, dissolved in anhydrous ODCB and 1,4-dioxane solvent by ultrasonic treatment, the sealed mixture is heated and stirred at 130°C for reaction, cooled to room temperature after the reaction stops, the insoluble matter is filtered out, the solvent is removed under reduced pressure, CS2 is used as an eluent to collect the unreacted [60]fullerene, and then the eluent is switched to CS2 / DCM to finally obtain the target product [60]fullerene-allylbenzofuran derivative. The reaction equation in the synthesis process is: Among them, the allyl oxide aryl iodide is The corresponding [60]fullerene-allylbenzofuran derivative is 2. The method for synthesizing [60]fullerene-allylbenzofuran derivatives catalyzed by palladium according to claim 1, characterized in that The molar ratio of the [60]fullerene, allyloxy aromatic iodide, Pd2(dba)3, 1,2-bis(diphenylphosphino)benzene and Cs2CO3 is 1:5:0.1:0.2:2.

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