A bisindole derivative and a process for its preparation

Abstract

The application discloses a kind of diindole derivatives and preparation method thereof, it is left-handed or right-handed optical active body or racemate with the following structural formula;Its preparation includes with isoindoline group propargyl alcohol compound and 2-indole methanol compound as raw material, with organic phosphoric acid catalyst as catalyst, reaction is obtained in organic solvent diindole derivative.The application utilizes catalytic tandem reaction method to synthesize diindole derivative, reaction condition is mild, process is simple, operation is convenient, the potential fluorescent property and biological activity of obtained product, this will have important significance to fluorescent material and synthesis drug screening.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of fluorescent synthesis, and particularly relates to a bisindole derivative and a preparation method thereof. BACKGROUND

[0002] Polycyclic aromatic hydrocarbon light-emitting molecules are widely used in blue OLED devices due to high photoluminescence efficiency and stable molecular structure. How to improve the device performance of such light-emitting molecules through molecular structure design has been a research direction that attracts much attention. Bisindole cyclopentane pyrrole derivatives are an important class of organic compounds, because the complex molecular structure contains two indole groups and pyrrole and cyclopentane, the introduction of lone pair electrons can not only improve the radiation transition rate of the molecule, but also increase the molar absorption coefficient of the molecule, which is conducive to the host-guest energy transfer in the device. In addition, studies have shown that the introduction of electron-deficient nitrogen atoms also helps to improve the horizontal emission dipole orientation ratio of the light-emitting layer, and thus improve the light extraction efficiency. These "nitrogen effects" are all conducive to improving the performance of blue OLED devices.

[0003]

[0004] Therefore, the synthesis of chiral bisindole derivatives has important exploratory significance in the field of fluorescent materials. SUMMARY

[0005] The purpose of the present application is to provide a bisindole derivative and a preparation method thereof.

[0006] The bisindole derivative of the present application is an optically active body or a racemate with the following structural formula:

[0007]

[0008] In the formula, R 3 ~ R 7 Each is independently selected from H, halogen, methyl, phenyl, substituted phenyl, naphthyl, cyclopropane, thienyl, and Ar is selected from phenyl, substituted phenyl, and thienyl. Among them, the substituents are all selected from halogen, methyl, ethyl, propyl, butyl, methoxy, and ethoxy.

[0009] The bisindole derivative is preferably one of the following structural formulas:

[0010]

[0011] The preparation method of the bisindole derivative of the present application comprises: using isoindoline-based propargyl alcohol compounds and 2-indole methanol compounds as raw materials, using 9-anthracene octahydrobinaphthalene phosphoric acid as a catalyst, reacting in an organic solvent at room temperature for 10-16 hours, and purifying to obtain the bisindole derivative.

[0012] The 9-anthracene octahydrobinaphthyl phosphoric acid is a compound with structural formula (1), which can be optically active or racemic:

[0013]

[0014] The isatinyl propargyl alcohol compound has the following formula (2):

[0015]

[0016] The 2-indole methanol compound has the following formula (3):

[0017]

[0018] In the present application, the isatinyl propargyl alcohol compound is preferably one of the following compounds:

[0019]

[0020] In the present application, the 2-indole methanol compound is preferably one of the following compounds:

[0021]

[0022] In the present application, the organic solvent is one or more of toluene, benzene, dichloromethane, 1,2-dichloroethane, fluorobenzene, chlorobenzene, 1,3-dichlorobenzene.

[0023] In the present application, the molar ratio of the 9-anthracene octahydrobinaphthyl phosphoric acid catalyst to the 2-indole methanol compound is 1-10:100, and the molar ratio of the isatinyl propargyl alcohol compound to the 2-indole methanol compound is 0.8-1.2:1; the reaction temperature is 15-35℃,

[0024] After the reaction is completed, the final product is separated and the catalyst is recovered by column chromatography, and the eluent for column chromatography is a mixture of ethyl acetate / petroleum ether, and the volume ratio of ethyl acetate / petroleum ether is further preferably 1:2-3.

[0025] The reaction equation of the present application is as follows:

[0026]

[0027] The bisindole derivative has good fluorescence performance and can be used as a fluorescent material.

[0028] Compared with the prior art, the present application has the following advantages:

[0029] 1) No metal catalyst is required, and the reaction can be carried out under mild conditions;

[0030] 2) The isoindolyl propargyl alcohol and 2-indole methanol compounds are easy to prepare, which reduces the cost of preparing the final product;

[0031] 3) The bis-indole derivative with high optical activity can be obtained;

[0032] 4) The product has good fluorescence properties.

[0033] In summary, the bis-indole derivative is synthesized by using the catalytic tandem reaction method in the present application, the reaction condition is mild, the process is simple, the operation is convenient, and the obtained product has potential good fluorescence properties. BRIEF DESCRIPTION OF DRAWINGS

[0034] Figure 1 It is a fluorescence performance test result diagram of the compound in the present application, in which 3a is the compound in Example 1, 3c is the compound in Example 2, 3j is the compound in Example 3, 3aa is the compound in Example 4, and 3p is the compound in Example 5. DETAILED DESCRIPTION

[0035] The following examples will help to understand the present application, but are not limited to the content of the present application.

[0036] Example 1

[0037] 2-hydroxy-2-phenylethynyl-3-methylindole (0.1 mmol), (2-indolyl)-di-p-methoxyphenyl methanol (0.11 mmol), 9-anthracene octahydrobinaphthyl phosphonic acid (0.01 mmol) shown in the structural formula (1) described above, 5 mL of 1,3-dichlorobenzene is injected, and the reaction is carried out at room temperature for 16 hours. After the reaction is completed, the corresponding optical active bis-indole derivative is directly obtained by using silica gel column chromatography with ethyl acetate / petroleum ether = 1:3 as the eluent, and the yield is 93%; the product is characterized as follows:

[0038] Structural formula:

[0039]

[0040] Property: white solid;

[0041] m.p. 281-283℃;

[0042] Optical purity: 94% ee;

[0043] HPLC analysis condition: (Daiel Chiralpak column, same below) Chiralpak IB-3 (n-hexane / i-PrOH = 95 / 5, 1.0 mL / min), t R (minor) 6.017 min, t R(minor) 9.091 min;

[0044] Optical rotation: [α] D 20 = -101 ° (c 1.00, CH2Cl2);

[0045] 1 H NMR (400 MHz, CDC13) δ 8.21 (s, 1H), 8.03 - 7.97 (m, 1H), 7.62 (d, J = 7.2 Hz, 1H), 7.42 - 7.37 (m, 1H), 7.35 (d, J = 7.8 Hz, 1H), 7.25 - 7.20 (m, 2H), 7.18 - 7.03 (m, 7H), 7.02 - 6.91 (m, 3H), 6.82 (t, J = 7.8 Hz, 2H), 6.53 (s, 4H), 6.30 - 6.20 (m, 4H), 3.69 (s, 3H), 3.59 (s, 3H), 2.14 (s, 3H);

[0046] HRMS m / z (ESI + ): calcd for C 47 H 37 N2O2([M+H] + ) 661.2850, found 661.2840.

[0047] Example 2

[0048] Into a reaction flask was added 2-hydroxy-2-(4-bromophenyl)ethynyl-3- methylindole (0.1 mmol), (2-indolyl)-di-p-methoxyphenylmethanol (0.11 mmol), 9- anthracenyl octahydrobinaphthyl phosphonic acid (0.01 mmol) as shown in the above structural formula (1), 5 mL of 1,3-dichlorobenzene was injected, and the reaction was allowed to proceed at room temperature for 16 hours. After the reaction was completed, the reaction mixture was directly subjected to silica gel column chromatography using ethyl acetate / petroleum ether = 1:3 as an eluent to obtain the corresponding optically active bisindole derivative in a yield of 91%. The product was characterized as follows:

[0049] Structural formula:

[0050]

[0051] Property: white solid;

[0052] m.p. 295-397 °C;

[0053] Optical purity: 92% ee;

[0054] HPLC analysis conditions: Chiralpak IB-3 (n-hexane / i-PrOH = 95 / 5, 1.0 mL / min), tR (major) 9.749 min, t R (minor) 16.560 min;

[0055] Optical rotation: [α] D 20 = -172° (c 1.5, CH2Cl2);

[0056] 1 H NMR (400 MHz, CDC13) δ 8.22 (s, 1H), 8.07 - 7.95 (m, 1H), 7.64 (d, J = 7.6 Hz, 1H), 7.40 - 7.30 (m, 2H), 7.29 - 7.06 (m, 10H), 7.06 - 6.97 (m, 2H), 6.92 (d, J = 8.7 Hz, 2H), 6.57 (s, 3H), 6.28 (d, J = 9.0 Hz, 2H), 6.10 (d, J = 8.6 Hz, 2H), 3.74 (s, 3H), 3.59 (s, 3H), 2.18 (s, 3H);

[0057] HRMS m / z (ESI + ): calculated for C 47 H 36 BrN2O2([M+H] + ) 741.1934, found 741.1930.

[0058] Example 3

[0059] Into a reaction flask was added 2-hydroxy-2-(4-methoxyphenyl)ethynyl-3- methylindole (0.1 mmol), (2-indolyl)-di-p-methoxyphenylmethanol (0.11 mmol), 9- anthracenyl octahydrobinaphthylphosphonic acid (0.01 mmol) as shown in the above structural formula (1), 5 mL of 1,3-dichlorobenzene was injected, and the reaction was allowed to proceed at room temperature for 16 hours. After the reaction was completed, the reaction mixture was directly subjected to silica gel column chromatography using ethyl acetate / petroleum ether = 1:3 as the eluent to obtain the corresponding optically active bisindole derivative in a yield of 92%. The product was characterized as follows:

[0060] Structural formula:

[0061]

[0062] Property: light yellow solid;

[0063] m.p. 299-301 °C;

[0064] Optical purity: 91% ee;

[0065] HPLC analysis condition: Chiralpak IB-3 (n-hexane / i-PrOH = 95 / 5, 1.0 mL / min), t R (major) 23.650 min, t R (minor) 36.758 min;

[0066] Optical rotation: [a] D 20 = -84° (c 1.0, CH2Cl2);

[0067] 1 H NMR (400 MHz, CDC13) δ 8.09 (s, 1H), 7.98 (d, J = 7.8 Hz, 1H), 7.58 (d, J = 7.2 Hz, 1H), 7.32 (d, J = 7.6 Hz, 1H), 7.22 - 7.03 (m, 7H), 6.98 (d, J = 8.6 Hz, 2H), 6.90 - 6.83 (m, 1H), 6.74 (t, J = 7.7 Hz, 2H), 6.63 - 6.30 (m, 6H), 6.22 (d, J = 7.9 Hz, 4H), 3.66 (s, 3H), 3.61 (s, 3H), 3.51 (s, 3H), 2.17 (s, 3H);

[0068] HRMS m / z (ESI + ): calcd for C 48 H 39 N2O3 ([M+H] + ) 691.2955, found 691.2953.

[0069] Example 4

[0070] A reaction bottle was added with 2-hydroxy-2-phenylacetylenyl-3-methylindole (0.1 mmol), (2-indolyl) bis (3-thienyl) methanol (0.11 mmol), 9-anthracene octahydrobinaphthyl phosphonic acid shown in the above structural formula (1) (0.01 mmol), 5 mL of 1,3-dichlorobenzene was injected, and the reaction was carried out at room temperature for 16 hours. After the reaction was completed, direct silica gel column chromatography was carried out with ethyl acetate / petroleum ether = 1:5 as the eluent, and the corresponding optically active bisindole derivative was obtained with a yield of 92%; the product was characterized as follows;

[0071] Structural formula:

[0072]

[0073] Property: light yellow solid;

[0074] m.p. 288-290 °C;

[0075] Optical purity: 91% ee;

[0076] HPLC analysis conditions: Chiralpak AD-H (n-hexane / i-PrOH = 97 / 3, 1.0 mL / min), t R (major) 8.020 min, t R (minor) 10.245 min;

[0077] Optical rotation: [α] D 20 = -82° (c 0.8, CH2Cl2);

[0078] 1 H NMR(400MHz, CDCl3)δ8.07(s,1H),8.02–7.93(m,1H),7.61(d,J=7.6Hz,1H),7.39–7.31(m,2H),7.26–7.19(m,4H),7.17–7.00(m,6H),7. 00–6.89(m,2H),6.83(t,J=7.7Hz,2H),6.71(d,J=1.6Hz,1H),6.67–7.61(m,1H),6.43(d,J=1.6Hz,1H),6.34–6.14(m,3H),2.19(s,3H);

[0079] HRMS m / z(ESI + ): Calculated value C 41 H 29 N2S2([M+H) + 613.1767, detected value 613.1769.

[0080] Example 5

[0081] 2-Hydroxy-2-cyclopropaneethynyl-3-methylindole (0.1 mmol), (2-indole)-di-p-methoxyphenylmethanol (0.11 mmol), and 9-anthracene octahydronaphthyl phosphate (0.01 mmol) as shown in the aforementioned structural formula (1) were added to a reaction flask. 5 mL of 1,3-dichlorobenzene was injected, and the reaction was carried out at room temperature for 16 hours. After the reaction was complete, the product was directly precipitated by silica gel column chromatography with ethyl acetate / petroleum ether at a ratio of 1:5 as the eluent to obtain the corresponding optically active bisindole derivative in 78% yield. The product was characterized as follows:

[0082] Structural formula:

[0083]

[0084] Appearance: Pale yellow solid;

[0085] m.p. 252-254 °C;

[0086] Optical purity: 84% ee;

[0087] HPLC analysis condition: Chiralpak IB-3 (n-hexane / i-PrOH = 95 / 5, 1.0 mL / min), t R (major) 9.276 min, t R (minor) 12.604 min;

[0088] Optical purity: 84% ee; D 20 = -27.0° (c 1.0, CH2Cl2);

[0089] 1 H NMR (400 MHz, CDC13) δ 8.19 - 8.02 (m, 3H), 7.61 (d, J = 7.9 Hz, 1H), 7.39 (t, J = 7.6 Hz, 1H), 7.33 - 7.03 (m, 9H), 7.02 - 6.91 (m, 4H), 6.65 - 6.02 (m, 4H), 3.86 (s, 3H), 3.57 (s, 3H), 2.02 (s, 3H), 0.98 - 0.80 (m, 2H), 0.67 - 0.51 (m, 1H), -0.15 - -0.36 (m, 1H), -0.76 - -0.97 (m, 1H);

[0090] HRMS m / z (ESI + ): calcd for C 44 H 37 N2O2([M+H] + ) 625.2850, found 625.2851.

[0091] Example 6

[0092] Into a reaction flask was added 2-hydroxy-isopropyl-ethynyl-3-methylindole (0.1 mmol), (2-indolyl)-di-p-methoxyphenylmethanol (0.11 mmol), 9-anthracene octahydrobinaphthyl phosphonic acid (0.01 mmol) as shown in the above structural formula (1), 5 mL of 1,3-dichlorobenzene was injected, and the reaction was allowed to proceed at room temperature for 16 hours. After the reaction was completed, the reaction mixture was directly subjected to silica gel column chromatography using ethyl acetate / petroleum ether = 1:5 as an eluent to obtain the corresponding optically active bis-indole derivative in a yield of 84%. The product was characterized as follows:

[0093] Structural formula:

[0094]

[0095] Appearance: yellowish solid;

[0096] m.p. 243-245 °C;

[0097] Optical purity: 91% ee;

[0098] HPLC analysis condition: Chiralpak IB-3 (n-hexane / i-PrOH = 95 / 5, 1.0 mL / min), t R (major) 7.294 min, t R (minor) 9.195 min;

[0099] Optical rotation: [a] D 20 = -91 ° (c 1.0, CH2Cl2);

[0100] 1 H NMR (400 MHz, CDC13) δ 8.23 (d, J = 8.0 Hz, 1H), 8.13 (d, J = 8.2 Hz, 1H), 8.05 (s, 1H), 7.60 (d, J = 7.9 Hz, 2H), 7.37 (t, J = 7.6 Hz, 1H), 7.33 - 7.22 (m, 3H), 7.21 - 6.86 (m, 9H), 6.71 - 5.97 (m, 4H), 3.87 (s, 3H), 3.55 (s, 3H), 2.62 - 2.45 (m, 1H), 1.95 (s, 3H), 1.02 (d, J = 7.0 Hz, 3H), 0.37 (d, J = 6.9 Hz, 3H);

[0101] HRMS m / z (ESI + ): calcd for C 44 H 39 N2O2([M+H] + ) 627.3006, found 627.3015.

[0102] Example 7

[0103] Into a reaction vial was added 2-hydroxy-2-phenylethynyl-3-methylindole (0.1 mmol), (2-(5-iodo)-indolyl)-di-p-methoxyphenyl-methanol (0.11 mmol), 9-anthracene octahydrobinaphthyl phosphonic acid (0.01 mmol) as shown in the above structural formula (1), 5 mL of 1,3-dichlorobenzene was injected, and the reaction was allowed to proceed at room temperature for 16 hours. After the reaction was completed, the reaction mixture was directly subjected to silica gel column chromatography using ethyl acetate / petroleum ether = 1:5 as the eluent to obtain the corresponding optically active bis-indole derivative in a yield of 88%. The product was characterized as follows:

[0104] Structural formula:

[0105]

[0106] Appearance: white solid;

[0107] m.p. 313-315 °C;

[0108] Optical purity: 91% ee;

[0109] HPLC analysis conditions: Chiralpak IB-3 (n-hexane / i-PrOH = 90 / 10, 1.0 mL / min), t R (major) 7.944 min, t R (minor) 13.612 min;

[0110] Optical rotation: [a] D 20 = -162° (c 1.0, CH2Cl2);

[0111] 1 H NMR 8.28 (s, 1H), 8.15 (s, 1H), 7.61 (d, J = 7.8 Hz, 1H), 7.42 (d, J = 8.5 Hz, 1H), 7.23 (s, 1H), 7.16 (s, 1H), 7.12 - 7.00 (m, 7H), 7.00 - 6.90 (m, 3H), 6.81 (t, J = 7.7 Hz, 2H), 6.50 (s, 4H), 6.26 - 6.14 (m, 4H), 3.66 (s, 3H), 3.54 (s, 3H), 2.13 (s, 3H);

[0112] HRMS m / z (ESI + ): calcd for C 47 H 36 IN2O2([M+H] + ) 787.1816, found 787.1807.

[0113] Example 8

[0114] Into a reaction flask was added 2-hydroxy-2-phenylethynyl-3-phenylindole (0.1 mmol), (2-indolyl)-di-p-methoxyphenyl-methanol (0.11 mmol), 9-anthracene octahydrobinaphthyl phosphonic acid (0.01 mmol) as shown in the above structural formula (1), 5 mL of 1,3-dichlorobenzene was injected, and the reaction was allowed to proceed at room temperature for 16 hours. After the reaction was completed, the product was directly subjected to silica gel column chromatography using ethyl acetate / petroleum ether = 1:5 as the eluent to obtain the corresponding optically active bis-indole derivative in a yield of 86%. The product was characterized as follows:

[0115] Structural formula:

[0116]

[0117] Appearance: white solid;

[0118] m.p. 347-349 °C;

[0119] Optical purity: 90% ee;

[0120] HPLC analysis conditions: Chiralpak IB-3 (n-hexane / i-PrOH = 90 / 10, 1.0 mL / min), t R (major) 5.557 min, t R (minor) 7.488 min;

[0121] Optical rotation: [a] D 20 = -58° (c 1.0, CH2Cl2);

[0122] 1 H NMR 8.10 (s, 1H), 8.03 (d, J = 7.0 Hz, 1H), 7.81 (d, J = 7.9 Hz, 1H), 7.50 (d, J = 8.1 Hz, 1H), 7.42 (d, J = 8.0 Hz, 1H), 7.32 - 7.16 (m, 12H), 7.11 (d, J = 7.3 Hz, 1H), 7.01 - 6.93 (m, 2H), 6.92 - 6.88 (m, 3H), 6.87 - 6.81 (m, 2H), 6.78 (d, J = 8.5 Hz, 1H), 6.60 - 6.27 (m, 6H), 5.83 (d, J = 34.3 Hz, 2H), 3.68 (s, 3H), 2.98 (s, 3H);

[0123] HRMS m / z (ESI + ): calcd for C 56 H 41 N2O2([M+H] + ) 773.3163, found 773.3133.

[0124] Fluorescence assay:

[0125] The skeleton of the compound bisindole derivative can be used for new functional materials, and is a structural unit with high application value, and its application can include organic light emitting diode, electroluminescent material and organic transistor, etc. Therefore, we study the fluorescence spectral properties of some obtained compounds. First, the fluorescence spectrum of the compound in a dilute dichloromethane solution (concentration c = 10 -5Fluorescence spectra (mol / L). The compounds tested in liquid fluorescence exhibited maximum fluorescence emission wavelengths in DCM solution between 430-465 nm. Figure 1 In compound a), compared to 3a, compound 3p exhibits a redshift of approximately 35 nm in its maximum fluorescence emission wavelength due to the presence of a larger aromatic substituent. Furthermore, we also tested the fluorescence quantum yields of three selected compounds. Figure 1 In b), the highest quantum yield is 3aa, Φ F =0.55. The three compounds were photographed under a UV lamp (λex = 365 nm); 3a showed blue, while 3p and 3aa showed light green. Furthermore, we selected the solid-state fluorescence emission of compounds 3a and 3p. Figure 1 In Figure c), compounds 3a and 3p exhibit good fluorescence intensity in the solid state, with maximum fluorescence emission wavelengths at 412 and 440 nm, respectively. Furthermore, the UV absorption spectra of compounds 3a, 3p, and 3aa were also tested (Figure d). The maximum absorption wavelengths of these three compounds are between 340 and 360 nm, with corresponding Stokes shifts between 100 and 110 nm.

Claims

1. A bisindole derivative, characterized in that... It is a left-handed or right-handed optically active or racemic compound with the following structural formula; ， In the formula: R 3 ~R 7 Each of the following is independently selected from H, halogen, methyl, phenyl, phenyl with substituents, naphthyl, cyclopropane, thiophene, wherein the substituent is selected from halogen, methyl, ethyl, propyl, butyl, methoxy, ethoxy; Ar is selected from phenyl, phenyl with substituents, thiophene, wherein the substituent is selected from halogen, methyl, ethyl, propyl, butyl, methoxy, ethoxy.

2. The bisindole derivative according to claim 1, characterized in that... The structural formula is one of the following: 。 3. A bisindole derivative, characterized in that, It is a left-handed or right-handed optically active or racemic compound with the following structural formula; 。 4. A method for preparing the bisindole derivative according to claim 1 or 3, characterized in that, The reaction involves using isoindolinopropynyl propargyl compounds and 2-indole methanol compounds as raw materials, with 9-anthracene octahydronaphthyl phosphate as a catalyst, reacting in an organic solvent at room temperature for 10-16 hours, and purifying to obtain bisindole derivatives. The 9-anthracene octahydronaphthyl phosphate is a compound having the structural formula (1), and is a levorotatory or dextrorotatory optically active form or racemate: ， Equation (1) The structure of the isoindoline-propargyl alcohol compounds is shown in formula (2) below: ， Equation (2) The structure of the 2-indole methanol compound is shown in formula (3) below: ， Equation (3).

5. The method for preparing bisindole derivatives according to claim 4, characterized in that, The isoindoline-propargyl alcohol compounds mentioned are one of the following compounds: 。 6. The method for preparing bisindole derivatives according to claim 4, characterized in that, The 2-indole methanol compounds mentioned are one of the following compounds: 。 7. The method for preparing bisindole derivatives according to claim 4, characterized in that, The organic solvent is one or more of toluene, benzene, dichloromethane, 1,2-dichloroethane, fluorobenzene, chlorobenzene, and 1,3-dichlorobenzene.

8. The method for preparing bisindole derivatives according to claim 4, characterized in that, The molar ratio of the 9-anthracene octahydronaphthyl phosphate catalyst to the 2-indole methanol compound is 1-10:100; the molar ratio of the isoindolelinylpropargyl alcohol compound to the 2-indole methanol compound is 0.8-1.2:1, and the reaction temperature is 15-35℃.

9. The application of the bisindole derivative according to claim 1 or 3, characterized in that, The derivatives described above can be used as fluorescent materials.

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