CN111233616A

CN111233616A - Pyrenyl [4] helicene and synthesis method and application thereof

Info

Publication number: CN111233616A
Application number: CN201910919274.3A
Authority: CN
Inventors: 赵文暄; 庞子金; 杨光; 杜世娜; 朱世江; 王传增; 大和武彦
Original assignee: Shandong University of Technology
Current assignee: Shandong University of Technology
Priority date: 2019-09-26
Filing date: 2019-09-26
Publication date: 2020-06-05

Abstract

The invention discloses a synthetic method and application of pyrenyl [4] helicene, wherein R in the helicene taking pyrene as a matrix is one of hydrogen atom, methoxyl and cyano, and the series of compounds have potential application values in the fields of luminescent materials, chemical sensing, biological imaging and detection; the synthesis method has the advantages that the raw materials are simple to prepare, the performance is very stable, and special storage conditions are not needed; related reagents and solvents are common commercial reagents, so that the cost is low; the whole synthesis route is simple, the yield is high, and the pollution is less; the synthesis method comprises three steps of synthesis, extraction and purification. The compound is more environment-friendly and efficient through photochemical cyclization reaction compared with the traditional synthesis mode, so that the method is easier to apply and popularize industrially, and the compound has high-efficient luminous performance and a spiral structure and has good application prospect in the field of chiral luminescent materials.

Description

Pyrenyl [4] helicene and synthesis method and application thereof

Technical Field

The invention belongs to the technical field of luminescent materials, and particularly relates to pyrenyl [4] helicene and a synthesis method and application thereof.

Background

Spiroolefins, as polycyclic aromatic hydrocarbons, are a class of non-planar structures with extended pi-conjugated systems. As an organic material having excellent photoelectric properties, a synthetic method thereof has been attracting attention. The catalytic synthesis with metal catalyst is the most common, but the synthesis method has high cost and high toxicity, and the environmental protection benefit is poor, so in recent years, the photochemical synthesis method becomes an efficient, economic and green method for synthesizing spiroalkene. Meanwhile, pyrene and its derivatives have a great importance in the field of photoelectric materials, and have the advantages of good thermal stability, a larger pi-conjugated system, high electron carrying capacity and the like, so that pyrene and its derivatives are favored in the field of organic photoelectric materials. Therefore, the synthesis of pyrenyl spiroalkene organic compounds is expected to play a great research potential in the fields of photoelectric materials, chiral materials and the like.

Disclosure of Invention

The invention aims to overcome the defects in the prior art and provide a spiroalkene taking pyrene as a parent, and the series of compounds have great application potential in the fields of luminescent materials, biological imaging or detection and the like; the invention takes 7-tert-butyl-1, 3-diphenyl-5-aldehyde pyrene as a raw material, under the heating condition, a series of spiroalkene compounds taking pyrene as a matrix are prepared through Wittig reaction and photocyclization reaction, and a new method is provided for synthesizing pyrenyl luminescent materials.

In order to expand the types of traditional spiroalkene compounds, the structural formula of a spiroalkene taking pyrene as a parent is provided as follows:

wherein R is one of a hydrogen atom, a methoxyl group and a cyano group. The spiroalkene taking pyrene as a matrix has excellent photophysical properties and has the potential of being applied to the fields of luminescent materials or biological imaging, detection and the like.

In order to better prepare the spiroalkene which has excellent photoelectric property and takes pyrene as a parent, the technical scheme of the invention provides a pyrenyl [4] spiroalkene synthesis method, which comprises the following steps:

s1: synthesizing, namely preparing spiroalkene taking pyrene as a matrix by using 7-tert-butyl-1, 3-diphenyl-5-aldehyde pyrene through wittig reaction and photocyclization reaction, wherein the reaction formula is as follows:

s2: extracting, namely extracting the cooled reaction product for 2-3 times by using a good solvent after the reaction is finished, collecting an organic phase solution, washing the collected organic phase solution for 2-3 times by using saturated salt water in sequence, and drying anhydrous magnesium sulfate to obtain a mixed solution of a reaction crude product and the good solvent;

s3: and (3) purifying, namely distilling and carrying out column chromatography on the mixed solution of the reaction crude product and the good solvent in sequence to obtain a pure target product.

The raw materials used in the invention are simple to prepare, have very stable performance and do not need special storage conditions; related reagents and solvents are common commercial reagents, so that the cost is low; the whole synthesis route is simple, the yield is high, and the pollution is less.

In order to better prepare the compound 2a, the preferable technical scheme is that in the step S1, the molar ratio of benzyltriphenylphosphonium chloride, n-butyllithium and 7-tert-butyl-1, 3-diphenyl-5-aldehyde pyrene is 1-3: 1-3: 1, the solvent is tetrahydrofuran, the reaction temperature is 0-40 ℃, and the reaction time is 8-24 h.

In order to improve the utilization rate and the reaction efficiency of raw materials, a further preferable technical scheme is that the molar ratio of benzyltriphenylphosphonium chloride, n-butyllithium and 7-tert-butyl-1, 3-diphenyl-5-aldehyde pyrene in the step S1 is 2: 2: 1, the solvent is tetrahydrofuran, the reaction temperature is 25 ℃, and the reaction time is 16 h.

In order to improve the purification efficiency of the reaction product, the preferable technical scheme is that the stationary phase used for column chromatography in S3 is silica gel, the eluent is a mixed solution of hexane and chloroform, and the volume ratio of the hexane to the chloroform is 2-3: 1.

in order to better prepare the compound 3a, the preferable technical scheme is that the molar ratio of the 7-tert-butyl-1, 3-diphenyl-5-styryl pyrene to the elementary iodine in the step S1 is 1: 1-2, taking benzene as a solvent and propylene oxide as a catalyst, and carrying out the illumination reaction for 4-12 hours.

In order to improve the utilization rate and the reaction efficiency of raw materials, a further preferable technical scheme is that the molar ratio of the 7-tert-butyl-1, 3-diphenyl-5-styryl pyrene to the elemental iodine in the step S1 is 1: 1.5, taking benzene as a solvent and propylene oxide as a catalyst, and carrying out the illumination reaction for 8 hours.

In order to improve the purification efficiency of the reaction product, the preferred technical scheme is that the stationary phase used in column chromatography in step S3 is silica gel, the eluent is a mixed solution of hexane and chloroform, and the volume ratio of the hexane to the chloroform is 2-3: 1.

The application of pyrenyl [4] helicene in the fields of luminescent materials, chemical sensing, bioluminescent probes, biological imaging and detection, according to claim 1.

The invention has the advantages and beneficial effects that:

1. the invention provides the spiroalkene which has excellent luminescence property and takes pyrene as a matrix, and the variety of the traditional spiroalkene luminescent material is expanded; the series of compounds have potential application values in the fields of luminescent materials, chemical sensing, biological fluorescent probes, biological imaging and detection.

2. The invention prepares the spiroalkene taking pyrene as a matrix by performing wittig reaction and photocyclization reaction on the 7-tert-butyl-1, 3-diphenyl-5-aldehyde pyrene compound, and provides a new method for synthesizing pyrenyl spiroalkene luminescent materials.

3. The raw materials used in the synthesis method are simple to prepare, have very stable performance and do not need special storage conditions; related reagents and solvents are common commercial reagents, so that the cost is low; the whole synthesis route is simple, the yield is high, and the pollution is less; the synthesis method comprises three steps of synthesis, extraction and purification, simplifies the synthesis steps compared with the traditional spiroalkene compounds, and is easier to apply and popularize industrially.

Drawings

FIG. 1 is a structural formula of pyrenyl [4] helicene of the present invention;

FIG. 2 is a chemical reaction formula for synthesizing pyrenyl [4] helicene according to the present invention;

FIG. 3 is a chemical reaction scheme of example 1, Synthesis 2 a;

FIG. 4 is a nuclear magnetic hydrogen spectrum of the objective product 2a of example 1;

FIG. 5 is a nuclear magnetic hydrogen spectrum of the target product 2b of example 10;

FIG. 6 is a single crystal structure of the target product 2 b;

FIG. 7 is a nuclear magnetic hydrogen spectrum of the objective product 2c of example 11

FIG. 8 is the chemical equation for example 12 for the synthesis of pyrenyl [4] spiroalkene 3 a;

FIG. 9 is a nuclear magnetic hydrogen spectrum of the target product 3a of example 12;

FIG. 10 is a nuclear magnetic hydrogen spectrum of the target product 3b of example 17;

FIG. 11 is a nuclear magnetic hydrogen spectrum of the target product 3c of example 18;

Detailed Description

The following description of the embodiments of the present invention will be made with reference to the accompanying drawings. The following examples are only for illustrating the technical solutions of the present invention more clearly, and the protection scope of the present invention is not limited thereby. The procedures, conditions, reagents, test methods and the like for carrying out the present invention are general knowledge and common general knowledge in the art except for the contents specifically mentioned below, and the present invention is not particularly limited. The data given in the examples below include specific operating and reaction conditions and products. The purity of the product is identified by nuclear magnetism and high-resolution mass spectrometry, and accurate structural information of partial compounds is obtained by an X-ray single crystal diffractometer.

As shown in figure 1, R is one of hydrogen atom, methoxyl group and cyano group.

The synthesis method of the helicene with excellent luminescence property and taking pyrene as a matrix comprises the following steps:

s1: synthesizing, as shown in figure 2, preparing helicene taking pyrene as a parent by a wittig reaction and a photocyclization reaction of a 7-tert-butyl-1, 3-diphenyl-5-aldehyde pyrene compound;

The drugs used in this example are all commercially available chemical reagents.

Example 1

As shown in FIG. 3, in an example of synthesis of 7-tert-butyl-1, 3-diphenyl-5-styrylpyrene, benzyltriphenylphosphonium chloride (389mg,1.0mmol) was added to 5mL of a dry tetrahydrofuran solvent, and after dissolution, n-butyllithium (1.1mL,1.0mmol) was slowly added under protection of argon gas at 0 ℃, and the mixture was stirred for 10 minutes. 7-tert-butyl-1, 3-diphenyl-5-aldehyde pyrene (219mg,0.5mmol) dissolved in 10mL of dry tetrahydrofuran solvent was then added to the mixture, and after the addition was completed, the mixture was stirred at room temperature under argon atmosphere for 16 h. After completion of the reaction, the reaction mixture was poured into a large amount of ice water to quench the reaction, extracted twice with 40mL of methylene chloride, washed twice with 40mL of saturated brine, and then dried over an appropriate amount of anhydrous magnesium sulfate. Distilling the solution until a small amount of liquid remains, and passing the solution throughPerforming column chromatography with n-hexane/chloroform mixture (3: 1, volume ratio) as eluent, and separating to obtain yellow solid target product 2a with yield of 148mg and 58%. The melting point of the target product 2a is 194-195 ℃;¹H NMR(400MHz,CDCl₃):δ_H＝1.60 (s,9H,tBu),7.19(d,J＝15.9Hz,1H,-CH＝CH_a-),7.32(t,J＝14.7Hz,2H,Ar-H), 7.43(t,J＝16.0Hz,2H,Ar-H),7.47-7.50(m,2H,Ar-H),7.56(t,J＝8.0Hz,2H, Ar-H),7.58(t,J＝8.0Hz,2H,Ar-H),7.65(d,J＝7.4Hz,2H,Ar-H),7.68(d,J＝7.0 Hz,2H,Ar-H),7.73(d,J＝7.0Hz,2H,Ar-H),7.96(s,1H,pyrene-H),8.00(d,J＝ 15.2Hz,1H,-CH＝CHb-),8.03(d,J＝8.8Hz,1H,pyrene-H),8.19(d,J＝9.2Hz,1H, pyrene-H),8.25(s,1H,pyrene-H),8.43(s,1H,pyrene-H),8.54(s,1H,pyrene-H)ppm；¹³C NMR(100MHz,CDCl₃):δ_C＝32.04,35.41,118.73,122.61,122.79,123.59, 124.97,126.80,127.24,127.31,127.45,127.59,127.82,127.89,128.35,128.44, 128.75,129.31,129.92,130.62,130.67,131.44,132.16,134.65,137.08,137.31, 137.64,141.03,141.06,149.01ppm；FAB-MS:m/z calcd for C₄₀H₃₂512.2504[M+]； found512.2504[M⁺].

example 2

Example 2 differs from example 1 in that benzyltriphenylphosphonium chloride (198mg, 0.5mmol), n-butyllithium (1.1mL, 1mmol) and 7-tert-butyl-1, 3-diphenyl-5-aldehydic pyrene (219mg,0.5mmol) were charged, and the yield of the desired product 2a isolated as a yellow solid was 82 mg at 32%, the data tested being the same as in example 1.

Example 3

Example 3 differs from example 1 in that the charge of benzyltriphenylphosphonium chloride (593mg, 1.5mmol), the charge of n-butyllithium (1.1mL, 1mmol) and the charge of 7-tert-butyl-1, 3-diphenyl-5-aldehydic pyrene (219mg,0.5mmol), the yield of the desired product 2a isolated as a yellow solid was 151mg, 59% and the data tested were the same as in example 1.

Example 4

Example 4 differs from example 1 in that benzyltriphenylphosphonium chloride (389mg,1.0mmol), n-butyllithium (0.55mL, 0.5mmol) and 7-tert-butyl-1, 3-diphenyl-5-aldelyrene (219mg,0.5mmol), and the yield of the desired product 2a was isolated as a yellow solid 102mg at 40%, according to the test data of example 1.

Example 5

Example 5 differs from example 1 in that benzyltriphenylphosphonium chloride was dosed (389mg,1.0mmol), n-butyllithium was dosed (1.65mL, 1.5mmol) and 7-tert-butyl-1, 3-diphenyl-5-aldehydic pyrene was dosed (219mg,0.5mmol), and the isolated yield of the desired product 2a was 148mg in 58% yield as a yellow solid, as determined in example 1.

Example 6

Example 6 differs from example 1 in that benzyltriphenylphosphonium chloride was charged (389mg,1.0mmol), n-butyllithium was charged (1.1mL,1.0mmol) and 7-tert-butyl-1, 3-diphenyl-5-aldehydic pyrene was charged (219mg,0.5mmol), the reaction temperature was 0 deg.C, the yield of the desired product 2a was isolated as a yellow solid 120mg, 47% and the data were as in example 1.

Example 7

Example 7 differs from example 1 in that benzyltriphenylphosphonium chloride (389mg,1.0mmol), n-butyllithium (1.1mL, 1.mmol) and 7-tert-butyl-1, 3-diphenyl-5-aldelydpyrene (219mg,0.5mmol), the reaction temperature is 40 deg.C, the yield of the desired product 2a was 151mg and 59% isolated as a yellow solid, and the test data were the same as in example 1.

Example 8

Example 8 differs from example 1 in that benzyltriphenylphosphonium chloride (389mg,1.0mmol), n-butyllithium (1.1mL, 1.mmol) and 7-tert-butyl-1, 3-diphenyl-5-aldelyrene (219mg,0.5mmol) were dosed, the reaction time was 8h, the yield of the desired product 2a isolated as a yellow solid was 92mg, 36%, and the test data were the same as in example 1.

Example 9

Example 9 differs from example 1 in that benzyltriphenylphosphonium chloride (389mg,1.0mmol), n-butyllithium (1.1mL, 1.mmol) and 7-tert-butyl-1, 3-diphenyl-5-aldelyrene (219mg,0.5mmol) were dosed, the reaction time was 24h, the yield of the desired product 2a isolated as a yellow solid was 153mg, 60% and the data tested was the same as in example 1.

TABLE 1 reaction conditions and Experimental results for examples 1-9

The experimental results show that: the yields of target products of experimental examples 2-9 are all lower than or similar to those of example 1, and considering the mildness of reaction conditions and the economical efficiency of raw materials, the reaction conditions of example 1 are determined to be optimal, that is, the molar ratio of benzyltriphenylphosphonium chloride, n-butyllithium to 7-tert-butyl-1, 3-diphenyl-5-aldehyde pyrene is 2: 2: 1. The reaction temperature is 25 ℃ and the reaction time is 16 h.

Example 10

Example 10 is different from example 1 in that the R substituent of 7-tert-butyl-1, 3-diphenylpyrenes is methoxy, and the yield of the desired product 2b isolated as a yellow solid was 45% according to the reaction conditions of example 1. The melting point of the target product was measured to be 223-:

¹H NMR(400MHz,CDCl₃):δ_H＝1.60(s,9H,tBu),3.86(s,3H,OMe),6.97(d,J ＝12.0Hz,1H,Ar-H),7.14(d,J＝16.9Hz,1H,-CH＝CH_a-),7.46-7.50(m,2H,Ar-H), 7.54–7.59(m,6H,Ar-H),7.68(d,J＝8.0Hz,2H,Ar-H),7.73(d,J＝8.0Hz,2H, Ar-H),7.86(d,J＝16.0Hz,1H,-CH＝CH_b-),7.95(s,1H,pyrene-H),8.03(d,J＝8.0 Hz,1H,pyrene-H),8.19(d,J＝12.0Hz,1H,pyrene-H),8.24(s,1H,pyrene-H),8.40 (s,1H,pyrene-H),8.54(s,1H,pyrene-H)ppm；¹³C NMR(100MHz,CDCl₃):δ_C＝ 31.96,55.36,113.54,114.17,118.76,122.37,122.56,124.63 124.92,124.96,127.21, 127.27,127.57,127.88,128.03,128.34,128.42,129.30,129.86,130.01,130.52, 130.63,130.68,131.46,131.66,134.90,136.92,137.20,141.13,148.96,159.44ppm； FAB-MS:m/z calcd for C₄₁H₃₄O542.2610[M⁺]；found 542.2615[M⁺].

example 11

Example 11 is different from example 1 in that the R substituent of 7-tert-butyl-1, 3-diphenylpyrene compounds is cyano, and the reaction conditions of example 1 are followed, and the yield of the target product 2c isolated as a yellow solid is 78%. The melting point of the target product was determined to be 263-265 ℃, the target product 2c was recrystallized and the nuclear magnetic data were determined as follows:

¹H NMR(400MHz,CDCl₃):δ_H＝1.61(s,9H,tBu),7.17(d,J＝16.0Hz,1H, -CH＝CH_a-),7.47-7.52(m,2H,Ar-H),7.56(t,J＝8.0Hz,2H,Ar-H),7.59(t,J＝8.0 Hz,2H,Ar-H),7.67-7.73(m,6H,Ar-H),7.97(s,1H,pyrene-H),8.04(d,J＝8.0Hz, 1H,pyrene-H),8.11(d,J＝16.0Hz,1H,-CH＝CH_b-),8.20(d,J＝12.0Hz,1H, pyrene-H),8.27(s,1H,pyrene-H),8.43(s,1H,pyrene-H),8.49(s,1H,pyrene-H) ppm；¹³C NMR(100MHz,CDCl₃):δC＝31.97,110.80,118.44,122.88,123.58, 125.12,127.20,127.38,127.97,128.39,129.44,129.44,130.23,130.60,130.67, 132.57,149.24ppm；FAB-MS:m/z calcd for C₄₁H₃₁N537.2457[M⁺]；found 537.2454[M⁺].

example 12

As shown in FIG. 7, in the example of synthesis of pyrenyl [4] spiroalkene 3a, 7-tert-butyl-1, 3-diphenyl-5-styrylpyrene (150mg,0.29mmol), benzene (250mL), propylene oxide (3.9mL, 55mmol), elemental iodine (112mg, 0.44mmol) were added to a photochemical reactor, and the reaction was performed under light for 8 hours. After the reaction is finished, the reaction solution is concentrated and purified by column chromatography, a mixed solution of n-hexane and chloroform (3: 1, volume ratio) is used as an eluent, a yellow solid target product 3a is obtained by separation, and the yellow solid target product is obtained by further recrystallization in a mixed solution of dichloromethane and methanol, wherein the yield is 13mg, and the yellow solid is 8%.

¹H NMR(400MHz,CDCl₃):δH＝1.58(s,9H,t-Bu),6.89(d,J＝8.0Hz,1H, Ar-H),6.33(d,J＝8.0Hz,1H,Ar-H),7.46(t,J＝8.0Hz,2H,Ar-H),7.15(t,J＝8.0 Hz,2H,Ar-H),7.54(t,J＝8.0Hz,2H,Ar-H),7.67(d,J＝8.0Hz,3H,Ar-H),7.96(t, J＝12.0Hz,2H,Ar-H),8.01(d,J＝8.0Hz,1H,Ar-H),8.04(s,1H,Ar-H),8.11(d,J＝ 8.0Hz,1H,Ar-H),8.16(s,1H,Ar-H),8.79(d,J＝8.0Hz,1H,Ar-H),8.94(s,1H, Ar-H)ppm；¹³C NMR(100MHz,CDCl₃):δC＝31.93,118.10,120.34,122.64, 123.09,124.38,124.72,125.12,126.29,126.35,127.30,127.35,127.40,128.22, 128.49,129.36,129.54,129.95,130.08,130.34,130.44,131.13,131.78,138.01, 138.56,143.98,149.25ppm；FAB-MS:m/z calcd for C₄₀H₃₀510.2348[M⁺]；found 510.2383[M⁺].

Example 13

Example 13 differs from example 12 in that 7-tert-butyl-1, 3-diphenyl-5-styrylpyrene was fed (150mg,0.29mmol), elemental iodine was fed (75mg, 0.29mmol), propylene oxide as a catalyst was fed (3.9mL, 55mmol), benzene as a solvent was fed (250mL), and the reaction was carried out with light for 8 hours. The desired product 3a was isolated as a yellow solid in a yield of 8mg in a yield of 5% according to the same test data as in example 12.

Example 14

Example 14 differs from example 12 in that 7-tert-butyl-1, 3-diphenyl-5-styrylpyrene was fed (150mg,0.29mmol), elemental iodine was fed (150mg, 0.6mmol), propylene oxide as a catalyst was fed (3.9mL, 55mmol), benzene as a solvent was fed (250mL), and the reaction was carried out with light for 8 hours. The desired product 3a was isolated as a yellow solid in 13mg yield of 8% according to the same test data as in example 12.

Example 15

Example 15 differs from example 12 in that 7-tert-butyl-1, 3-diphenyl-5-styrylpyrene was fed (150mg,0.29mmol), elemental iodine was fed (112mg, 0.44mmol), propylene oxide as a catalyst was fed (3.9mL, 55mmol), benzene as a solvent was fed (250mL), and the reaction was carried out with light for 4 hours. The desired product 3a was isolated as a yellow solid in a yield of 7mg in a yield of 4% according to the same test data as in example 12.

Example 16

Example 16 differs from example 12 in that 7-tert-butyl-1, 3-diphenyl-5-styrylpyrene was fed (150mg,0.29mmol), elemental iodine was fed (112mg, 0.44mmol), propylene oxide as a catalyst was fed (3.9mL, 55mmol), benzene as a solvent was fed (250mL), and the mixture was reacted with light for 12 hours. The desired product 3a was isolated as a yellow solid in 14mg yield and 9% yield, according to the same test data as in example 12.

Table 2 reaction conditions and Experimental results for examples 12 to 16

The experimental results show that: the yields of the target products of the experimental examples 12 to 16 are all lower than or similar to those of the experimental example 12, and considering the mildness of the reaction conditions and the economic efficiency of the raw materials, the optimal reaction conditions of the experimental example 12 are determined, namely the feeding amount of 7-tert-butyl-1, 3-diphenyl-5-styryl pyrene is (150mg,0.29mmol), the feeding amount of elemental iodine is (112mg, 0.44mmol), the feeding amount of the catalyst propylene oxide is (3.9mL, 55mmol), the feeding amount of the solvent benzene is 250mL, and the light irradiation reaction is carried out for 8 hours.

Example 17

Example 17 differs from example 12 in that the R substituent in 7-tert-butyl-1, 3-diphenylpyrenes is methoxy, and the reaction conditions of example 11 were followed, and the yield of the desired product 3b isolated as a yellow solid was 8%. The melting point of the target product was measured to be 141-:

¹H NMR(400MHz,CDCl₃):δ_H＝1.64(s,9H,tBu),3.74(s,3H,OMe),6.87(dd, J＝2.4,2.0Hz,1H,Ar-H),6.99(d,J＝4.0Hz,3H,Ar-H),7.22(s,1H,Ar-H),7.50(t,J ＝8.0Hz,2H,Ar-H),7.57-7.64(m,3H,Ar-H),7.74(d,J＝4.0Hz,2H,Ar-H),7.95(d, J＝8.0Hz,1H,Ar-H),7.99(d,J＝8.0Hz,1H,Ar-H),8.10(s,1H,Ar-H),8.17(d,J＝ 8.0Hz,1H,Ar-H),8.20(s,1H,Ar-H),8.70(d,J＝8.0Hz,2H,Ar-H),8.98(s,1H, Ar-H)ppm；¹³C NMR(100MHz,CDCl₃):δ_C＝30.89,53.97,108.48,115.81,117.08, 117.23,121.70,122.04,123.63,125.32,125.59,126.14,126.31,126.43,126.89, 127.06,127.46,127.79,128.49,129.01,129.40,129.55,130.15,130.92,136.86, 139.87,142.62,148.25,155.80ppm；FAB-MS:m/z calcd for C₃₀H₂₈O 540.2453[M⁺]； found 540.2453[M⁺].

example 18

Example 18 differs from example 12 in that the R substituent in the 7-tert-butyl-1, 3-diphenylpyrene compound is cyano and the reaction conditions of example 11 were followed, and the yield of the isolated target product 3c was 13% as a yellow solid. The melting point of the target product was measured to be 138 ℃, the target product 3c was recrystallized and the nuclear magnetic data were measured as follows:

¹H NMR(400MHz,CDCl₃):δ_H＝1.65(s,1H,tBu),7.01(t,J＝8.0Hz,1H, Ar-H),7.29(d,J＝8.0Hz,1H,Ar-H),7.51-7.68(m,5H,Ar-H),7.73(t,J＝8.0Hz, 3H,Ar-H),8.01(d,J＝4.0Hz,1H,Ar-H),8.03(d,J＝4.0Hz,1H,Ar-H),8.14(d,1H, Ar-H),8.20(d,J＝8.0Hz,1H,Ar-H),8.26(s,1H,Ar-H),8.98(d,J＝8.0Hz,1H, Ar-H),8.99(s,1H Ar-H)ppm；¹³C NMR(100MHz,CDCl₃):δ_C＝30.87,107.00, 117.27,122.68,122.91,123.89,124.68,125.79,126.57,127.54,129.36,129.72, 134.63,142.30,148.59ppm；FAB-MS:m/z calcd forC₄₁H₂₉N 535.2300[M⁺]；found 535.2300[M⁺].

the experimental results show that: by adopting the synthetic method of pyrenyl [4] helicene, pyrenyl helicene compounds with substituent groups of hydrogen, methoxy and cyano respectively can be successfully synthesized.

The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the technical principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims

1. A synthetic method and application of pyrenyl [4] helicene are characterized in that the structural formula is as follows:

wherein R is one of a hydrogen atom, a methoxyl group and a cyano group.

2. A synthetic method of pyrenyl [4] helicene is characterized by comprising the following steps:

s1: synthesizing, namely preparing spiroalkene taking pyrene as a matrix by a wittig reaction and a photocyclization reaction of 7-tert-butyl-1, 3-diphenylpyrene derivatives, wherein the reaction formula is as follows:

3. The method for synthesizing the compound 2a according to claim 2, wherein in the step S1, the molar ratio of benzyltriphenylphosphonium chloride, n-butyllithium, and 7-tert-butyl-1, 3-diphenyl-5-aldepyrene is 1 to 3: 1-3: 1, the solvent is tetrahydrofuran, the reaction temperature is 0-40 ℃, and the reaction time is 8-24 h.

4. The method for synthesizing the compound 2a according to claim 3, wherein the molar ratio of benzyltriphenylphosphonium chloride, n-butyllithium and 7-tert-butyl-1, 3-diphenyl-5-aldepyrene in the step S1 is 2: 2: 1, the solvent is tetrahydrofuran, the reaction temperature is 25 ℃, and the reaction time is 16 h.

5. The method for synthesizing pyrenyl [4] helicenes according to claim 3, wherein the stationary phase used in the column chromatography in step S3 is silica gel, the eluent is a mixture of hexane and chloroform, and the volume ratio of hexane to chloroform is 2-3: 1.

6. the method for synthesizing the compound 3a according to claim 2, wherein the molar ratio of 7-tert-butyl-1, 3-diphenyl-5-styrylpyrene to elemental iodine in step S1 is 1: 1-2, taking benzene as a solvent and propylene oxide as a catalyst, and carrying out the illumination reaction for 4-12 hours.

7. The method of synthesizing the compound 3a according to claim 6, wherein the molar ratio of 7-tert-butyl-1, 3-diphenyl-5-styrylpyrene to elemental iodine in step S1 is 1: 1.5, taking benzene as a solvent and propylene oxide as a catalyst, and carrying out the illumination reaction for 8 hours.

8. The method for synthesizing a compound 3a according to claim 7, wherein the stationary phase used in the column chromatography in step S3 is silica gel, the eluent is a mixture of hexane and chloroform, and the volume ratio of hexane to chloroform is 2-3: 1.

9. the application of pyrenyl [4] helicene in the fields of luminescent materials, chemical sensing, bioluminescent probes, biological imaging and detection, according to claim 1.