CN106432316A - Indole piperazoisoindole or benzoindole piperazoisoindole derivative and synthesis method thereof - Google Patents

Abstract

The invention relates to an indole-azino-isoindole or benzindole-azino-isoindole derivative and a synthesis method thereof. This compound has the following structure: Wherein, R is methoxy, methyl, hydrogen, chlorine, nitro. Theoretically, the method undergoes a [8+2] cycloaddition reaction, which successfully constructs the indole-azino-isoindole or benzindole-azino-isoindole molecular skeleton, enriching the organic condensed Synthetic methods of cyclic compounds. Analyzed from the performance test, indole azinoisoindole or benzindole azinoisoindole derivatives have certain photoelectric properties, and some compounds have higher quantum yields. These compounds all exhibit strong blue or green fluorescence, and are organic light-emitting materials with potential application value.

Description

Indole azinoisoindole or benzindole azinoisoindole derivative and synthesis method thereof

technical field

The invention belongs to the field of heterocyclic compounds in organic chemistry, and relates to a condensed heterocyclic compound indole-azinoisoindole or a benzindole-azinoisoindole derivative and a synthesis method thereof.

Background technique

Indole azinoisoindole derivatives have very good fluorescence and high quantum yield, so they have potential application prospects in luminescent materials and sensors. Therefore, the synthesis of indole azinoisoindole derivatives has attracted everyone interest of. The [8+2] cycloaddition reaction is an important reaction for the synthesis of heterocyclic compounds, which has the characteristics of atom economy, and is also one of the hot spots in modern organic synthetic chemistry. The synthesis of indole azinoisoindole derivatives has been reported in the literature. In 2007, it was reported in the literature that o-trimethylsilylphenol trifluoromethanesulfonate was used as a benzyne precursor to form benzyne under the action of a fluorine reagent. The indoleazine and isoindole derivatives are synthesized by reacting the doxylazine derivatives, and the method is relatively simple. At present, we have studied the [8+2] cycloaddition reaction of benzobis(oxydisiloxane) with indolezine derivatives to form oxydisilazine at room temperature, which is a simple and convenient method. Oxydisilazindolazinoisoindole derivatives and dioxotrisilylindoleazinoisoindole derivatives were synthesized. At the same time, we discovered for the first time that oxydisilazylnaphthalene was used as a naphthalene precursor to form naphthalene at room temperature, and undergo [8+2] cycloaddition reaction with indoxazine derivatives to synthesize a new condensed heterocyclic benzo The indole-azino-isoindole derivative has a simple synthesis method and mild conditions. The photoelectric properties of oxodisilazindolazinoisoindole derivatives and benzindoleazinoisoindole derivatives were studied.

Invention content:

One of the objects of the present invention is to provide a new class of oxydisilazino-indole-azino-isoindole derivatives, dioxo-trisilyl-indole-azino-isoindole derivatives or benzindole-azino-isoindole derivatives derivative.

The second object of the present invention is to provide the preparation method of these derivatives.

For achieving the above object, the reaction process of the present invention is:

Benzobis(oxydisiloxane) (1) or oxydisilazyl naphthalene (7) reacts with iodophenyl diacetate and trifluoromethanesulfonic acid to generate phenyl [o(hydroxydimethylsilyloxydisila fused phenyl)]trifluorosulfonic acid iodide (2) or phenyl[o-(hydroxydimethylsilyl)naphthyl]trifluorosulfonic acid iodide (8). At room temperature, sequential addition of 2-arylindolezine derivatives 4a-e, cesium fluoride (CsF), first generates benzyne intermediate 3 or naphthyne intermediate 9, which is immediately derivatized with 2-aryl indolezine Compound 4a-e undergoes [8+2] cycloaddition reaction to generate oxydisilazinoindole azinoisoindole derivatives 5a-e and dioxotrisilyl indole azinoisoindole derivatives 6a-e , with a total yield of 42-63%; or benzindole-azino-isoindole derivatives 10a-e, with a yield of 42-72%.

According to above-mentioned reaction mechanism, the present invention adopts following technical scheme:

An indole-azino-isoindole or benzindole-azino-isoindole derivative, characterized in that the compound has one of the following structures:

, or

Wherein, R is methoxy, methyl, hydrogen, chlorine or nitro.

A method for preparing the above-mentioned indoleazinoisoindole or benzindoleazinoisoindole derivatives, characterized in that the method has the following steps:

a. Under the protection of inert gas, add trifluoromethanesulfonic acid to the dichloromethane solution of iodophenyl diacetate salt under the condition of ice-water bath, react in ice-water bath for 0.5-1 hour, and react in room temperature for 1-2 hours; ice-water bath Add the reaction solution to the dichloromethane solution of benzobis(oxydisiloxo) or oxydisilazylnaphthalene under certain conditions, continue to react in an ice-water bath for 0.5 to 1 hour, and react at room temperature for 3 to 4 hours. Extraction of phenyl[o(hydroxydimethylsilyloxydisilyl fused phenyl)]trifluorosulfonic acid iodide or phenyl[o(hydroxydimethylsilyl)naphthyl]trifluorosulfonic acid iodide , washed with water, dried and spin-off the solvent;

b. Under the protection of an inert gas, the dichloromethane solution of phenyl [o-(hydroxydimethylsilyl oxygen disilyl fused phenyl)] trifluorosulfonic acid iodide obtained in step a or phenyl [o-( Add the acetonitrile solution of hydroxydimethylsilyl) naphthyl] trifluorosulfonic acid iodide in batches to the dichloromethane solution or acetonitrile solution of 2-aryl indolezine derivatives and cesium fluoride, and reflux for 1 to 1.5 Hours, after separation and purification, the final product indole-azino-isoindole or benzindole-azino-isoindole derivatives are obtained;

The structural formula of the iodophenyl diacetate salt is: PhI(OAc) ₂ ;

The structural formula of the benzobis(oxydisiloxane) is: ;

The structural formula of described oxygen disilazyl naphthalene is: ;

Its structural formula of described phenyl [ortho (hydroxyl dimethylsilyl oxygen disilazyl fused phenyl)] trifluorosulfonic acid iodide is: ;

Its structural formula of described phenyl [ortho (hydroxyl dimethyl silyl) naphthyl] trifluorosulfonic acid iodide is: ;

The structural formula of described 2-aryl indolezine derivatives is: , wherein R is methoxy, methyl, hydrogen, chlorine or nitro;

The molar ratio of the iodine diacetate, trifluoromethanesulfonic acid, benzobis(oxydisiloxane) or oxydisilazine naphthalene, 2-aryl indolezine derivatives, and cesium fluoride (CsF) is : 1.0~1.5 : 2.5~3.0 : 1.0~1.2 : 0.5 : 9.5~10.0.

The method of the present invention uses benzobis(oxydisilazine) or oxydisilazine naphthalene as the precursor of benzyne or naphthyne, forms benzyne and naphthyne at room temperature, and further reacts with indolezine derivatives to generate oxygen Disilazinoindoleazinoisoindole derivatives and dioxotrisilylindoleazinoisoindole derivatives or benzindoleazinoisoindole derivatives. The synthesis method has the advantages of fast reaction speed, mild reaction conditions, and environmental friendliness.

The invention discloses a method for synthesizing indole oxazinoisoindole derivatives or benzoindole oxazinoisoindole derivatives. The aryne precursor, which forms benzyne or naphthyne under mild conditions, undergoes [8+2] cycloaddition reaction with 2-aryl indolezine derivatives respectively to obtain indoleazinoisoindole derivatives Or benzindole azinoisoindole derivatives. The synthesis method has the characteristics of fast reaction speed, mild reaction conditions and atom economy.

Theoretically, the method undergoes a [8+2] cycloaddition reaction, which successfully constructs the indole-azino-isoindole or benzindole-azino-isoindole molecular skeleton, enriching the organic condensed Synthetic methods of cyclic compounds.

Analyzed from the performance test, indole azinoisoindole or benzindole azinoisoindole derivatives have photoelectric performance, see Figure 1-4, Table 1-2, some compounds have higher quantum yield. These compounds all exhibit strong blue or green fluorescence, and are organic light-emitting materials with potential application value.

Description of drawings

Figure 1 Absorption spectra of compounds 5a-5e in dichloromethane solvent;

Figure 2 Absorption spectra of compounds 10a-10e in dichloromethane solvent;

Figure 3. Emission spectra of compounds 5a-e in dichloromethane solvent;

Fig. 4 Emission spectra of compounds 10a-e in dichloromethane solvent.

detailed description

Example 1: iodophenyl diacetate (1.0~1.5 eq), trifluoromethanesulfonic acid (2.5~3.0 eq), benzobis(oxydisiloxo) (1, 1.0~1.2 eq), 2-p-methyl Oxyphenylindoleazine (4a, 0.5 eq), cesium fluoride (9.5～10.0 eq), the obtained indoleazinoisoindole derivatives are: 1-p-methoxyphenyl-7,8-oxo Disilazino[3,4,5- ab ]isoindole (5a) and 1-p-methoxyphenyl-7,8-dioxotrisilazino[3,4, 5- ab ] isoindole (6a), the total yield was 54%. The structure of this compound is:

and

5a: Molecular formula: C ₂₅ H ₂₅ NO ₂ Si ₂

Chinese name: 1-p-methoxyphenyl-7,8- oxodisilazino [3,4,5-ab]isoindole

English name: 1- p -Methoxyphenyl-7,8- oxadisilole indolizino[3,4,5-ab ]isoindole

Molecular weight: 427.14

Melting point: 158-160 ℃

Appearance: yellow powder

¹ H NMR (500 MHz, CDCl ₃ ): δ 0.48 (s, 6H, SiMe ₂ ), 0.50 (s, 6H, SiMe ₂ ), 3.95 (s, 3H, OCH ₃ ), 7.17 (d , J = 8.5 Hz, 2H, Ar-H), 7.24 (s, 1H, Ar-H), 7.72 (t, J = 8.0 Hz, 1H, Ar-H), 8.01 (d, J = 9.0 Hz, 2H , Ar-H), 8.03 (d, J = 8.0 Hz, 1H, Ar-H), 8.12 (d, J = 7.5 Hz, 1H, Ar-H), 8.53 (s, 1H, Ar-H), 8.68 (s, 1H, Ar-H) ppm.

Carbon NMR: ¹³ C NMR (125 MHz, CDCl ₃ ): δ 1.3, 1.5, 55.4, 103.8, 107.7, 114.6, 115.0, 118.8, 120.0, 121.8, 125.3, 127.9, 128.8, 120.93, 139 , 131.6, 140.4, 147.3, 159.3 ppm.

: Molecular formula: C ₂₇ H ₃₁ NO ₃ Si ₃

Chinese name: 1-p-methoxyphenyl-7,8- dioxotrisilyl indole azino[3,4,5-ab]isoindole

English name: 1- p -Methoxyphenyl-7,8- dioxatrisilole indolizino[3,4,5-ab ]isoindole

Molecular weight: 501.16

Melting point: 176-177 ℃

Appearance: yellow powder

¹ H NMR (500 MHz, CDCl ₃ ): δ 0.17 (s, 6H, SiMe ₂ ), 0.55 (s, 6H,SiMe ₂ ), 0.57 (s, 6H, SiMe ₂ ), 3.95 (s , 3H, OCH ₃ ), 7.15 (d, J = 8.5 Hz, 2H, Ar-H), 7.264 (s, 1H, Ar-H), 7.73 (t, J = 8.0 Hz, 1H, Ar-H), 8.02-8.04 (m, 3H, Ar-H), 8.14 (d, J = 7.0 Hz, 1H, Ar-H), 8.66 (s, 1H, Ar-H), 8.67 (s, 1H, Ar-H) ppm.

Carbon Nuclear Magnetic Resonance Spectrum: ¹³ C NMR (125 MHz, CDCl ₃ ): δ 0.8, 2.2, 2.4, 55.5, 103.7, 108.1, 114.5, 115.0, 119.0, 120.1, 125.5, 127.8, 128.2, 128.3, 128.8, 128.6, , 129.7, 131.7, 138.4, 145.1, 159.3 ppm.

Example 2: iodophenyl diacetate (1.0~1.5 eq), trifluoromethanesulfonic acid (2.5~3.0 eq), benzobis(oxydisiloxo) (1, 1.0~1.2 eq), 2-p-methyl phenylindolezine (4b, 0.5 eq), cesium fluoride (9.5 ~ 10.0 eq), the obtained indole azinoisoindole derivatives are: 1-p-methylphenyl-7,8-oxodisilazine Indolazino[3,4,5- ab ]isoindole (5b) and 1-p-methylphenyl-7,8-dioxotrisilylindoleazino[3,4,5- ab ] Isoindole (6b), the total yield was 47%. The structure of this compound is:

and

5b: Molecular formula: C ₂₅ H ₂₅ NOSi ₂

Chinese name: 1-p-methylphenyl-7,8- oxodisilazino [3,4,5-ab]isoindole

English name: 1- p -Methylphenyl-7,8- oxadisilole indolizino[3,4,5-ab ]isoindole

Molecular weight: 411.15

Melting point: 167-169 °C

Appearance: yellow powder

¹ H NMR (500 MHz, CDCl ₃ ): δ 0.50 (s, 6H, SiMe ₂ ), 0.51 (s, 6H,SiMe ₂ ), 2.52 (s, 3H, CH ₃ ), 7.29 (s , 1H, Ar-H), 7.45 (d, J = 8.0 Hz, 2H, Ar-H),7.72 (t, J = 8.0 Hz, 1H, Ar-H), 7.99 (d, J = 8.0 Hz, 2H , Ar-H), 8.04 (d, J =8.0 Hz, 1H, Ar-H), 8.13 (d, J = 7.5 Hz, 1H, Ar-H), 8.57 (s, 1H, Ar-H), 8.69 (s, 1H, Ar-H) ppm.

Carbon NMR: ¹³ C NMR (125 MHz, CDCl ₃ ): δ 1.3,1.4, 21.3, 104.1, 107.8,115.1, 120.0, 122.0, 125.3, 128.0, 128.5, 128.9, 129.8, 129.9, 133.0, 133.0 , 135.0, 137.3, 140.5, 147.4 ppm.

: Molecular formula: C ₂₇ H ₃₁ NO ₂ Si ₃

Chinese name: 1-p-methylphenyl-7,8- dioxotrisilyl indole azino[3,4,5-ab]isoindole

English name: 1- p -Methylphenyl-7,8- dioxatrisilole indolizino[3,4,5-ab ]isoindole

Molecular weight: 485.17

Melting point: 157-159 °C

Appearance: yellow powder

¹ H NMR (500 MHz, CDCl ₃ ): δ 0.16 (s, 6H, SiMe ₂ ), 0.55 (s, 6H,SiMe ₂ ), 0.57 (s, 6H, SiMe ₂ ), 2.50 (s , 3H, CH ₃ ), 7.31 (s, 1H, Ar-H), 7.42 (d, J = 8.0 Hz, 2H, Ar-H), 7.73 (t, J = 8.0 Hz, 1H, Ar-H), 8.00 (d, J = 8.0 Hz, 2H, Ar-H), 8.04 (d, J = 8.5 Hz, 1H, Ar-H), 8.14 (d, J = 7.5 Hz, 1H, Ar-H), 8.66( s, 1H, Ar-H), 8.70 (s, 1H, Ar-H) ppm.

Carbon NMR: ¹³ C NMR (125 MHz, CDCl ₃ ): δ 0.8, 2.2, 2.4, 21.4, 104.0, 108.2, 115.2, 119.1, 120.1, 125.7, 127.9, 128.26, 128.32, 128.4, 129, 129 , 131.9, 133.1, 137.5, 138.5, 145.2 ppm.

Example 3: iodophenyl diacetate (1.0~1.5 eq), trifluoromethanesulfonic acid (2.5~3.0 eq), benzobis(oxydisiloxo) (1, 1.0~1.2 eq), 2-phenyl Indolezine (4c, 0.5 eq), cesium fluoride (9.5～10.0 eq), the obtained indoleazinoisoindole derivatives are: 1-phenyl-7,8-oxodisilazinoindoleazino[ 3,4,5- ab ]isoindole (5c) and 1-phenyl-7,8-dioxotrisilylindoleazino[3,4,5- ab ]isoindole (6c), totaling The rate is 63%. The structure of this compound is:

and

5c: Molecular formula: C ₂₄ H ₂₃ NOSi ₂

Chinese name: 1-phenyl-7,8- oxodisilazindole azino [3,4,5-ab]isoindole

English name: 1-Phenyl-7,8- oxadisilole indolizino[3,4,5-ab ]isoindole

Molecular weight: 397.13

Melting point: 173-175 ℃

Appearance: yellow powder

¹ H NMR (500 MHz, CDCl ₃ ): δ 0.50 (s, 6H, SiMe ₂ ), 0.52 (s, 6H,SiMe ₂ ), 7.31 (s, 1H, Ar-H), 7.48 ( t, J = 7.5 Hz, 1H, Ar - H), 7.64 (t, J = 7.5Hz, 2H, Ar-H), 7.73 (t, J = 8.0 Hz, 1H, Ar-H), 8.06 (d, J = 8.5 Hz, 1H, Ar-H), 8.10 (d, J = 7.5 Hz, 2H, Ar-H), 8.14 (d, J = 7.5 Hz, 1H, Ar-H), 8.57 (s,1H, Ar-H), 8.70 (s, 1H, Ar-H) ppm.

Carbon NMR spectrum: ¹³ C NMR (125 MHz, CDCl ₃ ): δ 1.3, 1.4, 104.4, 107.9, 115.3, 119.0, 120.1, 122.0, 125.3, 127.4, 128.1, 128.6, 128.8, 1230.13, 130.1, 130.1 , 136.3, 140.7, 147.5 ppm.

: Molecular formula: C ₂₆ H ₂₉ NO ₂ Si ₃

Chinese name: 1-phenyl-7,8- dioxotrisilylindole azino [3,4,5-ab]isoindole

English name: 1-Phenyl-7,8- dioxatrisilole indolizino[3,4,5-ab ]isoindole

Molecular weight: 471.15

Melting point: 186-188 ℃

Appearance: yellow powder

¹ H NMR (500 MHz, CDCl ₃ ): δ 0.18 (s, 6H, SiMe ₂ ), 0.56 (s, 6H,SiMe ₂ ), 0.59 (s, 6H, SiMe ₂ ), 7.34 (s , 1H, Ar-H), 7.46 (t, J = 7.5 Hz, 1H, Ar - H), 7.62 (t, J = 8.0 Hz, 2H, Ar-H), 7.74 (t, J = 8.0 Hz, 1H , Ar-H), 8.06 (d, J = 8.5 Hz, 1H, Ar-H), 8.11 (d, J = 7.5 Hz, 2H, Ar-H), 8.16 (d, J = 7.0 Hz,1H, Ar -H), 8.68 (s, 1H, Ar-H), 8.71 (s, 1H, Ar-H) ppm.

Carbon NMR spectrum: ¹³ C NMR (125 MHz, CDCl ₃ ): δ 0.8, 2.1, 2.4, 104.2, 108.3, 115.3, 119.2, 120.2, 121.7, 125.6, 127.6, 127.9, 128.3, 128.6, 129. , 133.0, 136.1, 138.7, 145.2 ppm.

Embodiment four:

Iodophenyl diacetate (1.0~1.5 eq), trifluoromethanesulfonic acid (2.5~3.0 eq), benzobis(oxydisiloxo) (1, 1.0~1.2 eq), 2-p-chlorophenylindole oxazine (4d, 0.5 eq), cesium fluoride (9.5 ~ 10.0 eq), the obtained indole azinoisoindole derivatives are: 1-p-chlorophenyl-7,8-oxodisilazino indole azino[ 3,4,5- ab ]isoindole (5d) and 1-p-chlorophenyl-7,8-dioxotrisilylindoleazino[3,4,5- ab ]isoindole (6d) , The yield is 42%. The structure of this compound is:

and

5d: Molecular formula: C ₂₄ H ₂₂ ClNOSi ₂

Chinese name: 1-p-chlorophenyl-7,8- oxodisilazindole azino [3,4,5-ab]isoindole

English name: 1- p -Chlorophenyl-7,8- oxadisilole indolizino[3,4,5-ab ]isoindole

Molecular weight: 431.09

Melting point: 192-193 ℃

Appearance: yellow powder

¹ H NMR (500 MHz, DMSO): δ 0.45 (s, 6H, SiMe ₂ ), 0.46 (s, 6H,SiMe ₂ ), 7.51 (s, 1H, Ar-H), 7.74 (d , J = 8.5 Hz, 2H, Ar-H), 7.87 (t, J = 8.0Hz, 1H, Ar-H), 8.11 (d, J = 8.5 Hz, 2H, Ar-H), 8.25 (d, J = 8.0 Hz, 1H, Ar-H), 8.44 (d, J = 7.5 Hz, 1H, Ar-H), 8.59 (s, 1H, Ar-H), 8.99 (s, 1H, Ar-H)ppm.

Carbon NMR spectrum: ¹³ C NMR (125 MHz, CDCl ₃ ): δ 1.3, 1.4, 104.3, 108.2, 115.4, 118.9, 120.3, 121.7, 125.3, 128.2, 128.8, 129.2, 129.8, 130.01, 130.01, 13 , 134.8, 140.9, 147.7 ppm.

: Molecular formula: C ₂₆ H ₂₈ ClNO ₂ Si ₃

Chinese name: 1-p-chlorophenyl-7,8- dioxotrisilyl indole azino[3,4,5-ab]isoindole

English name: 1- p -Chlorophenyl-7,8- dioxatrisilole indolizino[3,4,5-ab ]isoindole

Molecular weight: 505.11

Melting point: 179-181 ℃

Appearance: yellow powder

¹ H NMR (500 MHz, CDCl ₃ ): δ 0.17 (s, 6H, SiMe ₂ ), 0.55 (s, 6H,SiMe ₂ ), 0.58 (s, 6H, SiMe ₂ ), 7.29 (s , 1H, Ar-H), 7.57 (d, J = 8.0 Hz, 2H, Ar-H), 7.74 (t, J = 8.0 Hz, 1H, Ar-H), 8.01 (d, J = 8.5 Hz, 2H , Ar-H), 8.06 (d, J = 8.5 Hz, 1H, Ar-H), 8.16 (d, J = 7.5 Hz, 1H, Ar-H), 8.62 (s, 1H, Ar-H), 8.66 (s, 1H, Ar-H) ppm.

Carbon NMR spectrum: ¹³ C NMR (125 MHz, CDCl ₃ ): δ 0.8, 2.2, 2.4, 104.2, 108.5,115.5, 118.5, 119.1, 120.4, 125.3, 128.0, 128.4, 128.7, 129.27, 129. , 133.4, 134.6, 139.0, 145.5 ppm.

Example 5: iodophenyl diacetate (1.0~1.5 eq), trifluoromethanesulfonic acid (2.5~3.0 eq), benzobis(oxydisiloxane) (1, 1.0~1.2 eq), 2-p-nitrogen phenylindoleazine (4e, 0.5 eq), cesium fluoride (9.5～10.0 eq), the obtained indoleazinoisoindole derivatives are: 1-p-nitrophenyl-7,8-oxodisilazine indoleazino[3,4,5- ab ]isoindole (5e) and 1-p-nitrophenyl-7,8-dioxotrisilylindoleazino[3,4,5- ab ] Isoindole (6e), the total yield was 58%. The structure of this compound is:

and

5e: Molecular formula: C ₂₄ H ₂₂ N ₂ O ₃ Si ₂

Chinese name: 1-p-nitrophenyl-7,8- oxodisilazindole azino [3,4,5-ab]isoindole

English name: 1- p -Nitrophenyl-7,8- oxadisilole indolizino[3,4,5-ab ]isoindole

Molecular weight: 442.12

Melting point: 212-213 ℃

Appearance: red powder

Proton NMR spectrum: ¹ H NMR (500 MHz, CDCl ₃ ): δ 0.497 (s, 6H, SiMe ₂ ), 0.504 (s, 6H,SiMe ₂ ), 7.35 (s, 1H, Ar-H), 7.75- 7.79 (m, 1H, Ar-H), 8.10 (d, J = 8.5 Hz, 1H, Ar-H), 8.17 (d, J = 7.5 Hz, 1H, Ar-H), 8.20 (d, J = 8.5 Hz, 2H, Ar-H), 8.47(s, 1H, Ar-H), 8.48 (d, J = 7.5 Hz, 2H, Ar-H), 8.69 (d, J = 1.0 Hz, 1H, Ar-H )ppm.

Carbon NMR spectrum: ¹³ C NMR (125 MHz, CDCl ₃ ): δ 1.3, 1.4, 104.9, 108.8, 116.1, 119.4, 120.8, 121.6, 124.5, 125.5, 128.5, 128.6, 128.8, 120.30, 130.9, 13 , 143.1, 146.8, 148.3 ppm.

: Molecular formula: C ₂₆ H ₂₈ N ₂ O ₄ Si ₃

Chinese name: 1-p-nitrophenyl-7,8- dioxotrisilyl indole azino[3,4,5-ab]isoindole

English name: 1- p -Nitrophenyl-7,8- dioxatrisilole indolizino[3,4,5-ab ]isoindole

Molecular weight: 516.14

Melting point: 188-190 ℃

Appearance: red powder

¹ H NMR (500 MHz, CDCl ₃ ): δ 0.17 (s, 6H, SiMe ₂ ), 0.56 (s, 6H,SiMe ₂ ), 0.58 (s, 6H, SiMe ₂ ), 7.38 (s , 1H, Ar- H ), 7.78 (t, J = 8.0 Hz, 1H, Ar- H ), 8.10 (d, J = 8.0 Hz, 1H, Ar- H ), 8.19 (d, J = 7.5 Hz, 1H , Ar- H ), 8.22 (d, J = 9.0 Hz, 2H, Ar- H ), 8.45 (d, J = 8.5 Hz, 2H, Ar- H ), 8.61 (s, 1H, Ar- H ),8.67 (s, 1H, Ar- H ) ppm.

Carbon Nuclear Magnetic Resonance Spectrum: ¹³ C NMR (125 MHz, CDCl ₃ ): δ 0.8, 2.2, 2.3, 104.9, 109.2,116.2, 119.6, 121.0, 124.4, 125.2, 128.5, 128.56, 128.61, 128.98, 128.92, 128.9 , 139.9, 143.0, 146.1, 146.9 ppm.

Example 6: iodophenyl diacetate (1.0-1.5 eq), trifluoromethanesulfonic acid (2.5-3.0 eq), oxydisilazyl naphthalene (7, 1.0-1.2 eq), 2-p-methoxyphenyl Indolezine (4a, 0.5 eq), cesium fluoride (9.5 ~ 10.0 eq), the obtained benzindole azinoisoindole derivatives are: 1-p-methoxyphenyl benzindole azino[3 ,4,5- ab ] isoindole (10a), the yield was 68%. The structure of this compound is:

10a: Molecular formula: C ₂₅ H ₁₇ NO

Chinese name: 1-p-methoxyphenylbenzindole azino[3,4,5- ab ]isoindole

English name: 1- p -Methoxyphenyl benzo[ f ]indolizino[3,4,5 -ab ]isoindole

Molecular weight: 347.13

Melting point: 215-217 ℃

Appearance: yellow powder

¹ H NMR (500 MHz, CDCl ₃ ): δ 3.97 (s, 3H, OCH ₃ ), 7.15 (s, 1H,Ar-H), 7.20 (d, J = 8.5 Hz, 2H, Ar -H), 7.53-7.56 (m, 1H, Ar-H), 7.59-7.64 (m,2H, Ar-H), 7.95 (d, J = 8.5 Hz, 1H, Ar-H), 8.01 (d, J = 7.0 Hz, 1H, Ar-H),8.05-8.06 (m, 2H, Ar-H), 8.13 (d, J = 8.5 Hz, 1H, Ar-H), 8.16 (d, J = 8.5 Hz, 1H, Ar-H), 8.76 (s, 1H, Ar-H), 8.95 (s, 1H, Ar-H) ppm.

Carbon NMR spectrum: ¹³ C NMR (125 MHz, CDCl ₃ ): δ 55.5, 102.5, 106.1, 114.6, 115.4, 116.5, 118.8, 119.9, 121.9, 124.5, 126.2, 128.37, 6, 128.41, 128.85 , 129.7, 129.91, 129.94, 130.1, 133.4, 159.1 ppm.

Example 7: iodophenyl diacetate (1.0~1.5 eq), trifluoromethanesulfonic acid (2.5~3.0 eq), oxydisilazyl naphthalene (7, 1.0~1.2 eq), 2-p-methylphenylind Oxyrazine (4b, 0.5 eq), cesium fluoride (9.5～10.0 eq), the resulting benzindole azinoisoindole derivatives are: 1-p-methylphenylbenzindole azino[3,4 ,5- ab ] isoindole (10b), yield 54%. The structure of this compound is:

10b: Molecular formula: C ₂₅ H ₁₇ N

Chinese name: 1-p-methylphenylbenzindole azino[3,4,5- ab ]isoindole

English name: 1- p -Methylphenyl benzo[ f ]indolizino[3,4,5 -ab ]isoindole

Molecular weight: 331.14

Melting point: 195-196 °C

Appearance: yellow powder

¹ H NMR (500 MHz, CDCl ₃ ): δ 2.52 (s, 3H, CH ₃ ), 7.19 (s, 1H,Ar-H), 7.47 (d, J = 8.0 Hz, 2H, Ar-H), 7.53-7.56 (m, 1H, Ar-H), 7.59-7.64 (m,2H, Ar-H), 7.96 (d, J = 8.5 Hz, 1H, Ar-H), 8.01-8.03 (m, 3H, Ar-H), 8.12 (d, J = 8.5 Hz, 1H, Ar-H), 8.16 (d, J = 8.0 Hz, 1H, Ar-H), 8.78 (s, 1H, Ar- H), 8.95 (s, 1H, Ar-H) ppm.

Nuclear magnetic resonance carbon spectrum: ¹³ C NMR (125 MHz, CDCL ₃ ): Δ 21.4, 102.8, 106.2, 114.1,115.6, 116.7, 119.0, 120.9, 124.5, 128.36, 128.45, 128.8, 129.3 , 129.7, 129.8, 130.10, 130.14, 133.4, 137.1 ppm.

Embodiment eight:

Iodophenyl diacetate (1.0~1.5 eq), trifluoromethanesulfonic acid (2.5~3.0 eq), oxydisilazyl naphthalene (7, 1.0~1.2eq), 2-phenylindolezine (4c, 0.5 eq ), cesium fluoride (9.5～10.0 eq), the obtained benzindole azinoisoindole derivatives are: 1-phenylbenzindole azino[3,4,5- ab ]isoindole (10c ), with a yield of 72%. The structure of this compound is:

10c: Molecular formula: C ₂₄ H ₁₅ N

Chinese name: 1-phenylbenzindole azino[3,4,5- ab ]isoindole

English name: 1-Phenyl benzo[ f ]indolizino[3,4,5 -ab ]isoindole

Molecular weight: 317.12

Melting point: 198-200 ℃

Appearance: yellow powder

¹ H NMR (500 MHz, CDCl ₃ ): δ 7.22 (s, 1H, Ar-H), 7.46-7.49 (m, 1H, Ar-H), 7.54-7.57 (m, 1H, Ar-H) -H), 7.59-7.62 (m, 1H, Ar-H), 7.63-7.67 (m,3H, Ar-H), 7.98 (d, J = 8.5 Hz, 1H, Ar-H), 8.02 (d, J = 7.0 Hz, 1H, Ar-H), 8.12-8.14 (m, 3H, Ar-H), 8.16 (d, J = 8.0 Hz, 1H, Ar-H), 8.78 (s, 1H, Ar-H ), 8.95 (s, 1H, Ar-H) ppm.

Carbon NMR spectrum: ¹³ C NMR (125 MHz, CDCl ₃ ): δ 103.0, 106.3, 115.7, 116.7, 119.1, 120.0, 121.9, 124.6, 126.2, 127.3, 128.40, 128.41, 128.5, 129.8, 129.8 , 129.9, 130.0, 130.1, 133.4, 136.3 ppm.

Example 9: iodophenyl diacetate (1.0-1.5 eq), trifluoromethanesulfonic acid (2.5-3.0 eq), oxydisilazyl naphthalene (7, 1.0-1.2 eq), 2-p-chlorophenylindole oxazine (4d, 0.5 eq), cesium fluoride (9.5 ~ 10.0 eq), the obtained benzindole azizoisoindole derivatives are: 1-p-chlorophenyl benzindole azino[3,4,5 - ab ] Isoindole (10d), yield 56%. The structure of this compound is:

10d: Molecular formula: C ₂₄ H ₁₄ ClN

Chinese name: 1-p-chlorophenylbenzindole azino[3,4,5- ab ]isoindole

English name: 1- p -Chlorophenyl benzo[ f ]indolizino[3,4,5 -ab ]isoindole

Molecular weight: 351.08

Melting point: 212-213 ℃

Appearance: yellow powder

¹ H NMR (500 MHz, CDCl ₃ ): δ 7.16 (s, 1H, Ar-H), 7.54-7.57 (m, 1H, Ar-H), 7.60-7.62 (m, 3H, Ar-H) -H), 7.63 (d, J = 7.0 Hz, 1H, Ar-H), 7.96 (d, J = 8.5 Hz, 1H, Ar-H), 8.01 (d, J = 7.0 Hz, 1H, Ar-H ), 8.02-8.04 (m, 2H, Ar-H), 8.11 (d, J = 8.5 Hz, 1H, Ar-H), 8.15 (d, J = 8.0 Hz, 1H, Ar-H), 8.69 (s ,1H, Ar-H), 8.93 (s, 1H, Ar-H) ppm.

Carbon NMR spectrum: ¹³ C NMR (125 MHz, CDCl ₃ ): δ 102.9, 106.5, 115.8, 116.5, 119.1, 120.3, 122.0, 124.7, 126.4, 128.2, 128.38, 128.43, 128.6, 129.8, 129.8 , 129.8, 130.1, 133.1, 133.4, 134.8 ppm.

Example 10: Iodophenyl diacetate (1.0-1.5 eq), trifluoromethanesulfonic acid (2.5-3.0 eq), oxydisilazyl naphthalene (7, 1.0-1.2 eq), 2-p-nitrophenylind Oxyrazine (4e, 0.5 eq), cesium fluoride (9.5～10.0 eq), the obtained benzindole azinoisoindole derivatives are: 1-p-nitrophenyl-benzindole azino[3, 4,5- ab ] isoindole (10e), yield 42%. The structure of this compound is:

10e: Molecular formula: C ₂₄ H ₁₄ N ₂ O ₂

Chinese name: 1-p-nitrophenylbenzindole azino[3,4,5- ab ]isoindole

English name: 1- p -Nitrophenylbenzo[ f ]indolizino[3,4,5 -ab ]isoindole

Molecular weight: 362.11

Melting point: 197-199 ℃

Appearance: red powder

¹ H NMR (500 MHz, CDCl ₃ ): δ 7.25 (s, 1H, Ar-H), 7.58-7.61 (m, 1H, Ar-H), 7.65-7.68 (m, 2H, Ar-H) -H), 8.00 (d, J = 8.5 Hz, 1H, Ar-H), 8.05 (d, J = 7.0 Hz, 1H, Ar-H), 8.15 (d, J = 8.5 Hz, 1H, Ar-H ), 8.17 (d, J = 8.0 Hz,1H, Ar-H), 8.24-8.26 (m, 2H, Ar-H), 8.49-8.51 (m, 2H, Ar-H), 8.72 (s, 1H, Ar-H), 8.96 (s, 1H, Ar-H) ppm.

Carbon Nuclear Magnetic Resonance Spectrum: ¹³ C NMR (125 MHz, CDCl ₃ ): δ 103.5, 107.1, 114.1, 116.3, 116.8, 119.7, 120.9, 122.3, 124.5, 125.1, 126.7, 128.5, 128.7, 128.9, , 129.91, 130.9, 133.45, 133.53, 139.3 ppm.

^[a] Measured in dichloromethane solvent. ^[b] Maximum absorption wavelength. ^[c] Maximum emission wavelength. ^[d] 0.1NH ₂ SO ₄ quinine solution is the standard (Φ ₃₆₅ = 0.54) test. ^[e] Decomposition temperature is measured by thermogravimetric analysis, under the protection of nitrogen, the heating rate is 10 ^o C/min.

^[a] Determination of oxidation potential ( E _ox ) in acetonitrile solvent by cyclic voltammetry, platinum electrode as working electrode, platinum wire as auxiliary electrode, saturated calomel electrode (SCE) as reference electrode, agar salt bridge, 0.1 M Tetrabutylammonium hexafluorophosphate was used as the electrolyte, ferrocene (vacuum dissociation energy -4.8 eV) was used as the external standard, the scan rate was 100 mV/s, E _1/2 (Fc/Fc ⁺ )=0.43V. ^[b] HOMO = -[ E _ox – [ E _1/2 (Fc/Fc ⁺ )] + 4.8]. ^[c] The energy level difference Eg is estimated from the UV absorption in dichloromethane. ^[d] LUMO = HOMO + Optical band gap.

Claims (2)

1. a kind of indolizine iso-indoles or benzindole piperazine isoindole derivatives it is characterised in that this compound have as follows One of structure：

、Or

Wherein, R is methoxyl group, methyl, hydrogen, chlorine or nitro.

2. a kind of prepare indolizine according to claim 1 and iso-indoles or benzindole piperazine isoindole derivatives Method is it is characterised in that the method has following steps：

A. under the protection of noble gases, ice-water bath condition, trifluoromethanesulfonic acid is added to the dichloromethane of iodobenzene diacetate salt In solution, ice-water bath reacts 0.5～1 hour, room temperature reaction 1～2 hour；Under the conditions of ice-water bath, this reaction solution is added to benzene And it is double（Oxygen two silicon cyclopentadienyl）Or in the dichloromethane solution of oxygen two silicon substrate naphthalene, continue ice-water bath and react 0.5～1 hour, room temperature reaction 3 ～4 hours, with dichloromethane extraction phenyl [adjacent (hydroxyl dimethyl silicon substrate oxygen two silicon substrate fused phenyl)] three fluosulfonic acid iodide, Or phenyl [adjacent (hydroxyl dimethyl silicon substrate) naphthyl] three fluosulfonic acid iodide, wash, be dried and revolve solvent；

B. under inert gas shielding, by step a gained phenyl [adjacent (hydroxyl dimethyl silicon substrate oxygen two silicon substrate fused phenyl)] three The dichloromethane solution of fluosulfonic acid iodide or the acetonitrile of phenyl [adjacent (hydroxyl dimethyl silicon substrate) naphthyl] three fluosulfonic acid iodide Solution by portions is added in dichloromethane solution or the acetonitrile solution of 2- (hetero) aryl indole oxazine derivatives and cesium fluoride, flows back 1～1.5 Hour, separated purification, obtain end-product indolizine and iso-indoles or benzindole piperazine isoindole derivatives；

The structural formula of described iodobenzene diacetate salt is：PhI(OAc)₂；

Described benzo is double（Oxygen two silicon cyclopentadienyl）Structural formula be：；

The structural formula of described oxygen two silicon substrate naphthalene is：；

Described phenyl [adjacent (hydroxyl dimethyl silicon substrate oxygen two silicon substrate fused phenyl)] three its structural formula of fluosulfonic acid iodide are：；

Described phenyl [adjacent (hydroxyl dimethyl silicon substrate) naphthyl] three its structural formula of fluosulfonic acid iodide are：；

The structural formula of described 2- (hetero) aryl indole oxazine derivatives is：, wherein R is methoxyl group, first Base, hydrogen, chlorine or nitro；

Described oxalic acid iodine salt, trifluoromethanesulfonic acid, benzo are double（Oxygen two silicon cyclopentadienyl）Or oxygen two silicon substrate naphthalene, 2- (hetero) aryl indole piperazine spread out Biological, cesium fluoride（CsF）Mol ratio be：1.0～1.5:2.5～3.0: 1.0~1.2 : 0.5 :9.5～10.0.