A method for preparing n-terminal alkenyl azaheteroarenes

Abstract

The application discloses a preparation method of N-terminal alkenyl azaheteroarene, which comprises the following steps: carrying out one-pot reaction of aromatic aldehyde and azaheteroarene under the action of alkali in an atmospheric atmosphere and dimethyl sulfoxide solvent, and obtaining N-terminal alkenyl azaheteroarene compound. The alkenyl of the N-terminal alkenyl azaheteroarene compound obtained by the method is derived from the raw material aldehyde, but one double bond carbon atom is added compared with the original aldehyde raw material. In the reaction process, the carbon-oxygen double bond of the raw material aromatic aldehyde is converted into carbon-carbon double bond, and the hydrogen atom on the carbonyl carbon of the aromatic aldehyde is replaced by the nitrogen atom in the azaheteroarene molecule. The method has the advantages of wide and easy raw material source, green environmental protection, low price and simple operation, and is favorable for industrialized production.

Description

Technical Field

[0001] This invention relates to a method for preparing N-terminated alkenyl azirroarynes, and particularly to a method for synthesizing N-terminated alkenyl azirroarynes by one-pot reaction of aromatic aldehydes and azirroarynes in dimethyl sulfoxide, belonging to the field of organic synthesis. Background Technology

[0002] N-terminal alkenyl azirnes are a class of special structural compounds with terminal alkenyl groups attached to the nitrogen atoms of azirnes. These molecules simultaneously possess both azirne and enamine structures, making them valuable and rare organic synthesis intermediates and raw materials for polymer synthesis. Furthermore, N-terminal alkenyl azirnes also exist in organisms and exhibit excellent physiological activities. The presence of the N-terminal alkenyl double bond in N-terminal alkenyl azirnes makes their synthesis relatively difficult. Currently, there are three main methods for synthesizing N-terminal alkenyl azirnes:

[0003] One method is the reaction of terminal alkynes with azaarones:

[0004]

[0005] This method requires gold and copper catalysis, and the products are a mixture of N-non-terminated alkenyl azirroreas and N-terminated alkenyl azirroreas, with the proportion of N-terminated alkenyl azirroreas being very small.

[0006] The second method is to react terminal haloalkenes with nitrogen-containing aromatic hydrocarbons:

[0007]

[0008] This method requires the catalysis of the precious metal Pd, and the raw materials need to be haloolefins. Except for haloethylene, most haloolefins require special preparation methods, and the source of raw materials is difficult to obtain.

[0009] A third method for synthesizing N-terminated alkenyl azirnes involves reacting methyl aryl ketone p-toluenesulfonyl hydrazine as a starting material with azirnes under the catalysis of the noble metal Pd.

[0010]

[0011] The starting material for this reaction, methyl aryl ketone p-toluenesulfonyl hydrazine, is difficult to obtain, unstable, and the reaction yield is generally less than 40%.

[0012] The raw materials used in the above methods—terminated alkynes, terminal halogenated alkenes, or methyl aryl ketones—are not common basic chemical raw materials. The catalysts all require precious metals, and the reactions require special process conditions, making them unsuitable for industrial production. The number of carbon atoms in the N-terminated alkenyl group of the obtained product is the same as the number of carbon atoms in its raw material. Summary of the Invention

[0013] To address the shortcomings of existing methods for synthesizing N-terminated alkenyl azirromatic hydrocarbons, such as the difficulty in obtaining raw materials, the use of expensive metal catalysts, and harsh reaction conditions, the present invention aims to provide a method for synthesizing N-terminated alkenyl azirromatic hydrocarbons with one additional double-bonded carbon atom in a one-pot reaction under mild reaction conditions, using aromatic aldehydes and azirromatic hydrocarbons as raw materials and sulfoxides as solvents and reagents. This method utilizes widely available and readily available raw materials, is environmentally friendly, inexpensive, and simple to operate, making it suitable for industrial production.

[0014] To achieve the above-mentioned technical objectives, this invention provides a method for synthesizing N-terminal alkenyl azirromatic hydrocarbons. This method involves a one-pot reaction of aromatic aldehydes and azirromatic hydrocarbons as raw materials in the presence of a base in a DMF solution under atmospheric conditions to obtain the N-terminal alkenyl azirromatic hydrocarbon compound. In the product structure, the carbon-oxygen double bond of the aromatic aldehyde is transformed into a carbon-carbon double bond, and the hydrogen atom on the carbonyl carbon of the aromatic aldehyde is replaced by a nitrogen atom from the azirromatic hydrocarbon molecule. The resulting N-terminal alkenyl azirromatic hydrocarbon compound has one more double-bonded carbon atom in its alkenyl group compared to the original aldehyde raw material.

[0015] The aromatic aldehyde has the structure of Formula 1:

[0016]

[0017] The nitrogen-containing aromatic hydrocarbon has the structure of Formula 2:

[0018]

[0019]

[0020] The N-terminal alkenyl nitrogen-containing aromatic hydrocarbon has the structure of Formula 3:

[0021]

[0022] in,

[0023] In Formula 1, Ar is phenyl, naphthalene, thiophene, quinoline or their substituted derivatives, and the substituents on the aromatic ring can be one or more of hydrogen, methyl, ethyl, propyl, butyl, isobutyl, isopropyl, benzyl, cyclohexylmethyl, methoxy, and methylenedioxy, and the substituents can be located at different positions in the aromatic ring;

[0024] The aza-aromatic hydrocarbon in Formula 2 can be indole, aza-indole, imidazole, pyrazole, pyrrole, or their substituted derivatives. The substituent can be one or more of fluorine, chlorine, bromine, methyl, or methoxy. The nitrogen atom in the aza-indole can be located at different positions on the indole ring.

[0025] In aromatic aldehydes, the aryl group (Ar) forms p-π conjugation with the carbonyl group, significantly increasing the reactivity of the carbonyl carbon atom. Common Ar groups are phenyl, naphthalene, or substituted phenyl or substituted naphthalene. Substituted phenyl or substituted naphthalene rings can contain 1 to 3 substituents, preferably one. The position of the substituent is not limited and can be ortho, meta, or para. The choice of substituent on the aromatic ring has little impact on the synthesis of the target product, offering a wide range of options. These can be alkyl groups (such as short-chain alkyl groups from C1 to C5, specifically methyl, ethyl, propyl, isopropyl, isobutyl, etc.), halogen substituents (such as fluorine, chlorine, bromine, or iodine), cyano, nitro, amino, alkoxy (such as short-chain alkoxy groups from C1 to C5), or alkoxyacyl groups (such as methoxyformyl, ethoxyacyl). When Ar is selected from aromatic heterocyclic groups, it can be an aromatic heterocycle containing at least one of oxygen, nitrogen, or sulfur, such as common thiophene, furan, pyrrole, pyridine, and quinoline.

[0026] The most preferred aromatic aldehydes include: benzaldehyde, 2-methylbenzaldehyde, 3-methylbenzaldehyde, 4-methylbenzaldehyde, 3-fluorobenzaldehyde, 4-fluorobenzaldehyde, 4-chlorobenzaldehyde, 4-bromobenzaldehyde, 4-cyanobenzaldehyde, 4-nitrobenzaldehyde, 4-methoxybenzaldehyde, 4-acetylbenzaldehyde, 4-ethoxybenzaldehyde, 3-trifluoromethylbenzaldehyde, 1-furanaldehyde, 1-naphthaldehyde, 2-naphthaldehyde, 6-quinolinealdehyde, and 3-thiophenealdehyde.

[0027] In a preferred embodiment, the alkali comprises at least one inorganic or organic alkali, such as sodium hydroxide, potassium hydroxide, potassium carbonate, sodium tert-butoxide, or potassium tert-butoxide, with potassium hydroxide being preferred.

[0028] In the preferred embodiment, the molar ratio of aldehyde to nitrogen-containing aromatic hydrocarbons is 1:2.

[0029] The oxygen-containing atmosphere of this invention can be air or pure oxygen.

[0030] In a preferred embodiment, the reaction conditions are: under an air or oxygen atmosphere, at a temperature of 70–100°C, for 10–50 minutes. In a more preferred embodiment, the reaction conditions are: under an air atmosphere, at a temperature of 80°C, for 30 minutes.

[0031] In the synthesis of N-terminal alkenyl nitrogen-containing aromatic hydrocarbons of the present invention, dimethyl sulfoxide (DMSO) serves as both a solvent and a reaction substrate and can be used in large excess.

[0032] In a preferred embodiment, the product is separated and purified by column chromatography after the reaction is completed; the eluent used in the column chromatography is a mixed solvent of petroleum ether and ethyl acetate, wherein the volume ratio of petroleum ether to ethyl acetate is (20-40):1.

[0033] The method for synthesizing N-terminated alkenyl azirrocarbons proposed in this invention has the following reaction equation:

[0034]

[0035] The N-terminal alkenyl nitrogen-containing aromatic compounds obtained by this method have an aryl group derived from the aldehyde starting material, but with an additional double-bonded carbon atom compared to the original aldehyde starting material. The reaction principle can be explained by the process of benzaldehyde reacting with indole to produce N-(1-styryl)indole: Under alkaline conditions, benzaldehyde reacts with DMSO via an Aldol reaction to generate intermediate 1-methylthionyl-2-styrene A. Then, air oxidizes thionyl intermediate A to thionyl intermediate B. Subsequently, indole, acting as a nucleophile, undergoes nucleophilic addition with intermediate B to generate intermediate C. Finally, under alkaline conditions, intermediate C undergoes methylthionyl group departure to generate N-(1-styryl)indole, which has an additional carbon atom compared to the original aldehyde starting material. DMSO plays a crucial role in the formation of N-terminated alkenyl azirnes in this reaction: firstly, it provides a nucleophilic carbon atom to convert the carbon-oxygen double bond of the aldehyde into a carbon-carbon double bond; secondly, it provides a methyl thionyl group to the carbon atom of the double bond, which reverses the electrophilicity of the carbon-carbon double bond, giving it nucleophilic double bond properties, and also serves as an excellent leaving group. Intermediates A, B, and C in the above process can all be detected in the reaction system, and N-(1-styryl)indole can be obtained by using intermediates A, B, and C as starting materials, respectively.

[0036]

[0037] Experiments have shown that if ketones are used instead of aldehydes, products with the corresponding structures cannot be obtained.

[0038] Compared with existing synthesis methods and techniques, the present invention has the following advantages and effects:

[0039] 1) This invention is the first to realize the direct conversion of the carbon-oxygen double bond structure of aldehydes to the N-terminal alkenyl nitrogen-aromatic hydrocarbon structure, and the product is an N-terminal alkenyl nitrogen-aromatic hydrocarbon with one more carbon atom than the aldehyde compound raw material.

[0040] 2) This invention uses simple and common aldehydes, nitrogen-containing aromatic hydrocarbons, and DMSO as raw materials. The raw materials are widely available, low in cost, and meet the requirements of industrial production.

[0041] 3) The reaction process of the present invention is carried out at a lower temperature, with a shorter reaction time and a higher product yield, making it suitable for industrial production;

[0042] 4) The reaction process of this invention does not use toxic raw materials, solvents and additives, the reaction conditions are mild, and the solvent is also a reactant, which meets the requirements of green environmental protection.

[0043] 5) The synthesis process of this invention is carried out by a one-pot reaction, which has fewer reaction steps and is simple to operate. Example

[0044] The present invention will be further described in detail below with reference to specific embodiments, but the implementation of the present invention is not limited thereto. For process parameters not specifically noted, conventional techniques can be referred to.

[0045] Unless otherwise stated, all reactions were carried out in Schlenk tubes.

[0046] All reaction raw materials and solvents were obtained from commercial sources and used without further purification.

[0047] Product separation was performed using a silica gel column (silica gel particle size 300-400 mesh).

[0048] ¹H NMR (400 MHz) and ¹³C NMR (100 MHz) were performed using a Bruker ADVANCE III spectrometer with CDCl₃ as solvent and TMS as internal standard. Chemical shifts are expressed in parts per million (ppm), with 0.0 ppm of tetramethylsilane as the reference shift. The following abbreviations (or combinations thereof) are used to interpret multiplicity: s = singlet, d = doublet, t = triplet, q = quartet, m = multiplet, br = broad peak. The coupling constant J is expressed in Hertz (Hz). Chemical shifts are expressed in ppm, referencing the center line of deuterated chloroform at 77.0 ppm triplet or deuterated DMSO at 39.52 ppm seventet.

[0049] 1. Condition optimization experiment:

[0050] Taking the reaction of benzaldehyde and indole in DMF as an example, the influencing factors of alkali compounds, reaction temperature, time and other conditions were explored in order to seek the optimal reaction conditions.

[0051] The reaction route is as follows:

[0052]

[0053]

[0054] Reaction conditions: benzaldehyde (0.5 mmol), indole (1 mmol), base (2 mmol), and DMSO (2.5 mL). a GC yield using 1,4-dichloro as an internal standard.

[0055] 1) Selection of alkali compounds

[0056] Experiments show that the reaction must occur under strongly alkaline conditions. Without a base or in a weakly alkaline environment, the reaction is almost impossible, as shown in items 2 and 3 of Table 1. The reaction can occur in the presence of strongly alkaline inorganic or organic bases, but KOH is significantly more effective than other bases, as shown in items 1 and 4-5 of Table 1.

[0057] 2) Selection of reaction temperature

[0058] Reaction temperature is a crucial factor affecting the chemical reaction process. This invention examines the yield of the reaction at different temperatures within the temperature range of 70–90°C, as shown in items 5 and 8-9 of Table 1. Within the temperature range of 70–90°C, the yield of the target product increases with increasing temperature. However, the reaction yield no longer increases above 80°C. Therefore, 80°C is the optimal temperature for this reaction.

[0059] 3) Selection of reaction time

[0060] The effect of reaction time on reaction yield is shown in items 5-9 of Table 1. The reaction yield is highest when the reaction time is 30 minutes, and the reaction yield no longer increases with increasing reaction time.

[0061] 2. Implementation process:

[0062] Weigh 0.5 mmol of an aldehyde compound, 1.0 mmol of a nitrogen-containing aromatic hydrocarbon, and 2 equiv. KOH into a 25 mL sealed tube equipped with a stir bar, and add 2 mL of DMSO. Place the sealed tube in an oil bath at 80 °C and heat for 30 min. Remove the sealed tube, stop the reaction, and cool the reaction solution to room temperature. Add 6 mL of saturated NaCl aqueous solution and approximately 10 mL of ethyl acetate (EtOAc) to the reaction solution. After shaking and standing for several minutes, remove the upper organic phase. Repeat the extraction process three times with the lower liquid. Remove the water from the organic phase with anhydrous sodium sulfate. Evaporate the resulting mixture to dryness using a rotary evaporator, then purify it by column chromatography packed with silica gel. Calculate the yield.

[0063] 3. Implementation Results:

[0064]

[0065]

[0066] 3. Proton and carbon spectra of some products:

[0067] N-(1-Styryl)indole (1-(1-phenylvinyl)-1H-indole)(1).

[0068]

[0069] Yellow solid. 1 H NMR (400MHz, CDCl3) δ7.73–7.65(m,1H),7.46–7.31(m,5H),7.21(d,J=3.2Hz,1H),7.18–7.10(m,3H),6.65(d,J=3.2Hz,1H),5.61(s,1H),5.40(s, 1H).13CNMR(101MHz,CDCl3)δ144.95,137.00,136.40,129.26,129.10,1 28.65,128.54,126.90,121.96,120.90,120.16,111.85,108.06,103.06.

[0070] N-(1-o-tolyl)vinyl)indole(1-(1-(o-tolyl)vinyl)-1H-indole)(2).

[0071]

[0072] Yellow solid. 1 H NMR (400MHz, CDCl3) δ7.64–7.57(m,1H),7.44–7.42(m,1H),7.33–7.24(m,3H),7. 14-7.10(m,3H),7.01(s,1H),6.54(s,1H),5.49(s,1H),5.18(s,1H),1.83(s,3H). 13 C NMR (101MHz, CDCl3) δ145.27,137.45,136.93,135.62,130.63,130.01,129.65,129.05,1 27.47,126.03,122.22,120.99,120.35,111.71,106.62,103.59,19.19.HRMS(ESI):calcd for C17H15N:233.1204,found:233.1206.

[0073] N-(1-p-methoxystyryl)indole(1-(1-(4-methoxyphenyl)vinyl)-1H-indole)(3)

[0074]

[0075] Yellow solid. 1H NMR (400MHz, CDCl3) δ7.62(d,J=7.2Hz,1H),7.25–7.03(m,6H),6.79(d,J=8.0Hz,2H),6.57(s,1H),5.42(s,1H),5.21(s,1H),3.73(s,3H). 13 C NMR (101MHz, CDCl3) δ160.32,144.52,136.39,129.46,129.25,128.66,128.22,121.87,120.84,120.08,113.87,111.93,106.24,102.88,55.19.

[0076] N-(1-(3,4-methylenedioxyphenyl)vinyl)indole(1-(1-(benzo[d][1,3]dioxol-5-yl)vinyl)-1H-indole)(4)

[0077]

[0078] Yellow solid. 1 H NMR (400MHz, CDCl3) δ7.74–7.61(m,1H),7.23–7.07(m,4H),6.88–6.73(m,3H),6.62(d,J=3.2Hz,1H),5.99(s,2H),5.48(s,1H),5.27(s,1H). 13 C NMR (101MHz, CDCl3) δ148.45,147.97,144.56,136.39,131.31,129.25,128.67,121.97,121 .10,120.90,120.16,111.89,108.25,107.29,106.91,103.04,101.36.HRMS(EI):calcdfor C17H13NO2:263.0946,found:263.0942.

[0079] N-(1-p-fluorostyryl)indole(1-(1-(4-fluorophenyl)vinyl)-1H-indole)(5)

[0080]

[0081] White solid. 1H NMR (400MHz, CDCl3) δ7.65 (d, J = 5.3Hz, 1H), 7.33–7.28 (m, 1H), 7.18–6.97 (m, 7H), 6.63 (s, 1H), 5.61 (s, 1H), 5.41 (s, 1H). 13 C NMR (101MHz, CDCl3) δ162.94(d,J=246.5Hz),143.91,136.33,130.13(d,J=8.2Hz),129.27,128.50,122.61(d, J=2.8Hz), 122.15, 120.68 (d, J=67.9Hz), 116.08 (d, J=21.3Hz), 113.89 (d, J=22.7Hz), 111.68, 109.23, 103.42.

[0082] N-(1-m-chlorostyryl)indole(1-(1-(3-chlorophenyl)vinyl)-1H-indole)(6)

[0083]

[0084] Pale green solid. 1 H NMR (400MHz, CDCl3) δ7.68(d,J=5.6Hz,1H),7.38(d,J=5.2Hz,2H),7.30(d,J =10.2Hz,1H),7.17(d,J=8.8Hz,5H),6.66(s,1H),5.63(s,1H),5.44(s,1H). 13 C NMR (101MHz, CDCl3) δ143.76,138.94,136.30,134.68,129.85,129.28,129.23,128.45 ,126.96,125.15,122.19,121.03,120.37,111.68,109.24,103.49.HRMS(EI):calcdfor C16H12ClN:253.0658,found:253.0657.

[0085] N-(1-p-bromostyryl)indole (1-(1-(4-bromophenyl)vinyl)-1H-indole)(7)

[0086]

[0087] Yellow oily liquid. 1H NMR (400MHz, CDCl3) δ7.67–7.65(m,1H),7.47(d,J=8.4Hz,2H),7.21–7.04(m,6H),6.63(d,J=3.2Hz,1H),5.58(s,1H),5.39(s,1H). 13 C NMR (101MHz, CDCl3) δ144.07,136.26,135.95,131.80,129.30,128.51,128.49,123.33,122.14,121.02,120.34,111.76,108.61,103.41.

[0088] N-(1-p-trifluoromethylstyryl)indole(1-(1-(3-(trifluoromethyl)phenyl)vinyl)-1H-indole)(8)

[0089]

[0090] A pale green, oily liquid. 1 H NMR (400MHz, CDCl3) δ7.79–7.65(m,3H),7.64–7.56(m,2H),7.54–7.44(m,3H),7 .33(t,J=7.4Hz,1H),7.23(t,J=7.4Hz,1H),6.76–6.65(m,2H).HRMS(EI):calcd for C17H12F3N:253.0658,found:253.0657.

[0091] N-(1-(2-naphthalenylvinyl))indole(1-(1-(naphthalen-2-yl)vinyl)-1H-indole)(9)

[0092]

[0093] Yellow solid. 1 H NMR(400MHz, CDCl3)δ7.84–7.75(m,4H),7.67(d,J=8.0Hz,1H),7.51–7.41(m,3H) ,7.22(d,J=2.8Hz,1H),7.20–7.04(m,3H),6.65(s,1H),5.70(s,1H),5.45(s,1H). 13C NMR (101MHz, CDCl3) δ144.99,136.49,134.43,133.62,133.13,129.29,128.76,128.43,128.3 3,127.64,126.67,126.48,126.37,124.47,122.05,120.93,120.22,111.91,108.63,103.17.

[0094] N-(1-(2-thiophen-2-yl)vinyl)indole(1-(1-(thiophen-2-yl)vinyl)-1H-indole)(10)

[0095]

[0096] Yellow oily liquid. 1 H NMR (400MHz, CDCl3) δ7.65(d,J=8.0Hz,1H),7.29(d,J=4.0Hz,2H),7.24(s,1H),7.18–7.10( m,2H),6.96(t,J=3.6Hz,1H),6.89(s,1H),6.61(d,J=2.0Hz,1H),5.64(s,1H),5.27(s,1H). 13 C NMR (101MHz, CDCl3) δ140.60,138.86,136.46,129.07,128.42,127.52,126.6 5,126.30,122.05,120.94,120.29,111.58,107.96,103.09.HRMS(EI):calcd for C14H11NS:225.0612,found:225.0615.

[0097] N-(1-Styryl)-2-methylindole (2-methyl-1-(1-phenylvinyl)-1H-indole)(11)

[0098]

[0099] Yellow solid. 1 H NMR (400MHz, CDCl3) δ7.60 (d, J = 7.4Hz, 1H), 7.36–7.31 (m, 3H), 7.08–7.20 (m, 5H), 6.42 (s, 1H), 6.08 (s, 1H), 5.45 (s, 1H), 2.25 (s, 3H). 13C NMR (101MHz, CDCl3) δ142.88,138.01,137.09,137.01,128.88,128.67,128.28,125.65,121.00,119.92,119.49,113.62,110.48,101.26,13.05.

[0100] N-(1-Styryl)-3-methylindole (3-methyl-1-(1-phenylvinyl)-1H-indole)(12)

[0101]

[0102] Yellow solid. 1 H NMR (400MHz, CDCl3) δ7.64(d,J=7.2Hz,1H),7.50–7.32(m,5H),7.22–7.13(m,3H),7.00(s,1H),5.53(s,1H),5.36(s,1H),2.40(s,3H). 13 C NMR (101MHz, CDCl3) δ144.98,137.32,136.65,129.81,129.01,128.49,127.10,126.18,121.93,119.59,118.95,112.21,111.83,106.95,9.57.

[0103] N-(1-Styryl)-5-methoxyindole (5-methoxy-1-(1-phenylvinyl)-1H-indole)(13)

[0104]

[0105] Yellow solid. 1 H NMR (400MHz, CDCl3) δ7.44–7.31(m,5H),7.16(d,J=17.8Hz,2H),7.03(d,J=8.8Hz ,1H),6.79(d,J=8.8Hz,1H),6.57(s,1H),5.54(s,1H),5.36(s,1H),3.87(s,3H). 13 C NMR (101MHz, CDCl3) δ154.36,145.08,137.05,131.59,129.79,129.17,129.12,128.53,127.01,112.66,112.02,107.37,102.75,102.59,55.75.

[0106] N-(1-Styryl)-4-fluoroindole (4-fluoro-1-(1-phenylvinyl)-1H-indole)(14)

[0107]

[0108] Yellow solid. 1 H NMR (400MHz, CDCl3) δ7.48–7.31(m,5H),7.19(s,1H),7.06(dd,J=13.8,7.3Hz,1H), 6.95(d,J=8.2Hz,1H),6.85(t,J=8.9Hz,1H),6.77(s,1H),5.67(s,1H),5.44(s,1H). 13 C NMR (101MHz, CDCl3) δ157.50, 155.05, 144.80, 138.92 (d, J = 10.9Hz), 136.61, 129.28, 128.63, 126.79, 122.48 ( d,J=7.7Hz),118.23(d,J=22.5Hz),108.81,107.93(d,J=3.6Hz),104.96(d,J=18.8Hz),99.00.HRMS(EI):calcd for C16H12FN:237.0954,found:237.0958.

[0109] N-(1-Styryl)-5-bromoindole (5-bromo-1-(1-phenylvinyl)-1H-indole)(15)

[0110]

[0111] Yellow oily liquid. 1 H NMR (400MHz, CDCl3) δ7.76 (s, 1H), 7.40–7.31 (m, 3H), 7.25 (d, J = 7.2Hz, 2H), 7.16 (d,J=10.0Hz,2H),6.95(d,J=8.8Hz,1H),6.54(s,1H),5.59(s,1H),5.34(s,1H). 13 C NMR (101MHz, CDCl3) δ144.69,136.56,135.05,130.91,129.81,129.34,128.66,126.81,124.85,123.39,113.46,113.27,108.57,102.57.

[0112] N-(1-Styryl)-5-azaindole (1-(1-phenylvinyl)-1H-pyrrolo[3,2-c]pyridine)(16)

[0113]

[0114] Yellow solid. ¹H NMR (400 MHz, CDCl₃) δ 8.95 (s, ¹H), 8.21 (d, J = 5.8 Hz, ¹H), 7.39–7.33 (m, ³H), 7.26–7.20 (m, ³H), 6.98 (d, J = 5.8 Hz, ¹H), 6.70 (d, J = 2.8 Hz, ¹H), 5.64 (s, ¹H), 5.38 (s, ¹H). 13 C NMR (101MHz, CDCl3) δ144.08,143.98,141.20,139.97,136.06,129.47,128.69,126.73,125.90,125.86,108.94,106.85,102.42.HRMS(EI):calcd forC15H12N2:220.1000,found:220.0997.

[0115] N-(1-Styryl)-7-azaindole (1-(1-phenylvinyl)-1H-pyrrolo[2,3-b]pyridine)(17)

[0116]

[0117] Yellow solid. 1 H NMR (400MHz, CDCl3) δ8.34(d,J=3.6Hz,1H),7.95(d,J=7.8Hz,1H),7.40–7.27(m,5H),7.18( d,J=3.0Hz,1H),7.11(dd,J=7.2,5.1Hz,1H),6.54(d,J=3.0Hz,1H),5.77(d,J=11.0Hz,2H). 13 C NMR (101MHz, CDCl3) δ148.30,143.50,142.84,137.30,128.95,128.92,128.84,128.44,126.74,121.31,116.50,110.08,100.74.HRMS(EI):calcd for C15H12N2:220.1000,found:220.1003.

[0118] N-(1-Styryl)pyrrole (1-(1-phenylvinyl)-1H-pyrrole)(18)

[0119]

[0120] Yellow oily liquid. 1 H NMR (400MHz, CDCl3) δ7.46 (s, 5H), 6.90 (s, 2H), 6.36 (d, J = 0.8Hz, 2H), 5.26 (s, 1H), 5.17 (s, 1H). 13 C NMR (101MHz, CDCl3) δ146.34,136.96,129.03,128.29,127.81,121.00,109.34,103.11.

[0121] N-(1-Styryl)carbazole (9-(1-phenylvinyl)-9H-carbazole)(19)

[0122]

[0123] Yellow oily liquid. 1 H NMR (400MHz, CDCl3) δ8.19 (d, J = 7.6Hz, 2H), 7.43–7.30 (m, 11H), 6.12 (s, 1H), 5.65 (s, 1H). 13 C NMR (101MHz, CDCl3) δ142.70,140.80,136.34,129.03,128.70,126.20,125.82,123.40,120.14,119.78,112.85,110.84.

[0124] N-(1-Styryl)pyrazole (1-(1-phenylvinyl)-1H-pyrazole)(20)

[0125]

[0126] A colorless, oily liquid. 1 H NMR (400MHz, CDCl3) δ7.72–7.66(m,1H),7.51–7.49(m,1H),7.46–7.34(m,5H),6.36(t,J=1.9Hz,1H),5.60(s,1H),5.20(s,1H). 13C NMR (101MHz, CDCl3) δ145.77,140.84,135.83,129.62,129.21,128.43,127.99,106.46,104.94.

[0127] N-(1-Styryl)-2-azaindole (1-(1-phenylvinyl)-1H-indazole)(21)

[0128]

[0129] Yellow oily liquid. 1 H NMR (400MHz, CDCl3) δ8.18(s,1H),7.78(d,J=8.0Hz,1H),7.48–7.25(m,6H),7.21-7.15(m,2H),5.60(d,J=10.2Hz,2H). 13 C NMR (101MHz, CDCl3) δ145.26,139.91,136.37,135.22,129.17,128.52,127.24,126.66,124.93,121.34,121.06,111.44,108.21.

[0130] N-(1-Styryl)imidazole (1-(1-phenylvinyl)-1H-imidazole)(22)

[0131]

[0132] Yellow oily liquid. 1 H NMR (400MHz, CDCl3) δ7.65 (s, 1H), 7.47–7.30 (m, 5H), 7.13 (s, 1H), 7.03 (s, 1H), 5.31 (d, J = 10.8Hz, 2H). 13 C NMR (101MHz, CDCl3) δ143.20,137.14,135.58,129.70,129.54,128.71,127.22,119.29,106.43.

[0133] N-(1-Styryl)-3-azaindole (1-(1-phenylvinyl)-1H-benzo[d]imidazole)(23)

[0134]

[0135] Yellow solid. 1H NMR(400MHz, CDCl3)δ8.04(s,1H),7.85(d,J=8.0Hz,1H),7.43–7.35(m,3H),7.31–7 .26(m,3H),7.20(t,J=7.6Hz,1H),7.07(d,J=8.0Hz,1H),5.69(s,1H),5.46(s,1H). 13 C NMR (101MHz, CDCl3) δ143.73,143.00,142.14,135.23,133.74,129.74,128.83,126.69,123.44,122.68,120.35,111.71,109.48.

[0136] N-(1-Styryl)-1,2,3-triazole (1-(1-phenylvinyl)-1H-1,2,3-triazole)(24)

[0137]

[0138] Yellow oily liquid. 1 H NMR (400MHz, CDCl3) δ7.77(s,1H),7.61(s,1H),7.46–7.37(m,3H),7.31(d,J=6.8Hz,2H),5.79(s,1H),5.54(s,1H). 13 C NMR(101MHz, CDCl3)δ142.93,134.58,133.56,129.83,128.78,127.21,123.88,109.48.HRMS(EI):calcd for C10H9N3:171.0796,found:171.0794.

[0139] N-(1-Styryl)-1,2,4-triazole (1-(1-phenylvinyl)-1H-1,2,4-triazole)(25)

[0140]

[0141] Yellow oily liquid. 1 H NMR (400MHz, CDCl3) δ8.15(s,1H),8.04(s,1H),7.46–7.30(m,5H),5.68(s,1H),5.35(s,1H). 13C NMR(101MHz, CDCl3)δ152.22,143.14,142.72,134.28,129.79,128.74,127.57,107.58.HRMS(EI):calcd for C10H9N3:171.0796,found:171.0793.

[0142] N-(1-m-methoxystyryl)pyrazole (1-(1-(3-methoxyphenyl)vinyl)-1H-pyrazole)(26)

[0143]

[0144] A colorless, oily liquid. 1 H NMR (400MHz, CDCl3) δ7.68(s,1H),7.49(s,1H),7.30(t,J=7.9Hz,1H),6.98–6.91(m,3H),6.35(s,1H),5.60(s,1H),5.19(s,1H),3.79(s,3H). 13 C NMR (101MHz, CDCl3) δ159.57,145.61,140.86,137.22,129.66,129.47,120.49,114.82,113.67,106.47,105.04,55.25.HRMS(EI):calcd for C10H9N3:200.0950,found:200.0947.

[0145] N-(1-p-methoxystyryl)pyrazole (1-(1-(4-methoxyphenyl)vinyl)-1H-pyrazole(27)

[0146]

[0147] A colorless, oily liquid. 1 H NMR (400MHz, CDCl3) δ7.69(s,1H),7.52(s,1H),7.32(d,J=8.0Hz,2H),6.92(d,J=8.0Hz,2H),6.36(s,1H),5.51(s,1H),5.13(s,1H),3.83(s,3H). 13 CNMR(101MHz, CDCl3)δ160.23,145.34,140.61,129.47,129.18,128.15,113.70,106.24,103.50,55.14.

[0148] N-(1-(3,4-methylenedioxyphenyl)vinyl)pyrazole(1-(1-(benzo[d][1,3]dioxol-5-yl)vinyl)-1H-pyrazole)(28)

[0149]

[0150] A colorless, oily liquid. 1 H NMR (400MHz, CDCl3) δ7.66(s,1H),7.51(s,1H),6.87(d,J=8.0Hz,1H),6.80(d,J=7.2Hz,2H),6.34(s,1H),5.97(s,2H),5.46(s,1H),5.10(s,1H). 13 CNMR(101MHz, CDCl3)δ148.42,147.65,145.38,140.79,129.83,129.61,122.08,108.28,108.13,106.41,104.15,101.29.

[0151] N-(1-(2-thiophenevinyl))pyrazole(1-(1-(thiophen-3-yl)vinyl)-1H-pyrazole(29)

[0152]

[0153] Yellow solid. 1 H NMR (400MHz, CDCl3) δ7.68(s,1H),7.59(s,1H),7.38(s,1H),7.34(d,J=2.8Hz,1H),7.16(d,J=4.8Hz,1H),6.36(s,1H),5.51(s,1H),5.25(s,1H). 13 C NMR(101MHz, CDCl3)δ140.98,140.77,136.96,129.39,126.92,126.01,124.83,106.44,104.45.HRMS(EI):calcd for C12H10N2O2:214.0742,found:214.0746.

[0154] N-(1-(m-trifluoromethyl)styryl)pyrrole(1-(1-(3-(trifluoromethyl)phenyl)vinyl)-1H-pyrrole)(30)

[0155]

[0156] Yellow oily liquid. 1 H NMR(400MHz, CDCl3)δ7.63(s,1H),7.54(d,J=7.2Hz,1H),7.51–7.42(m,2H),7.36(d ,J=14.6Hz,1H),7.01(s,2H),6.60(d,J=14.6Hz,1H),6.32(s,2H).HRMS(EI):calcd for C13H10F3N:237.0765,found:237.0765.

Claims

1. A method for preparing N-terminated alkenyl nitrogen-containing aromatic hydrocarbons, characterized in that: Under atmospheric conditions and in the presence of a base, aromatic aldehydes or heteroaromatic aldehydes react with nitrogen-containing aromatic hydrocarbons in dimethyl sulfoxide to form N-terminated alkenyl nitrogen-containing aromatic hydrocarbons: The aromatic aldehyde or heteroaromatic aldehyde has the structure of Formula 1: ， The nitrogen-containing aromatic hydrocarbon has the structure of Formula 2: ， The N-terminal alkenyl nitrogen-containing aromatic hydrocarbon has the structure of Formula 3: ， Wherein, Ar is phenyl, naphthyl, thiophene, quinolinyl or their substituted derivatives, and the substituent on the Ar ring is one or more of methyl, ethyl, propyl, butyl, isobutyl, isopropyl, methoxy, and methylenedioxy, and the substituent can be located at different positions on the Ar ring; The aza-aromatic hydrocarbon of Formula 2 is an indole, aza-indole, imidazole, pyrazole, pyrrole or its substituted derivatives, wherein the substituent is one or more of fluorine, chlorine, bromine, methyl, or methoxy, and the nitrogen atom in the aza-indole can be located at different positions on the indole ring. The alkali is potassium hydroxide.

2. The method for preparing an N-terminated alkenyl nitrogen-containing aromatic hydrocarbon according to claim 1, characterized in that: The reaction temperature is 70-100℃.

3. The method for preparing an N-terminated alkenyl nitrogen-containing aromatic hydrocarbon according to claim 2, characterized in that: The reaction temperature is 80℃.

4. The method for preparing an N-terminated alkenyl nitrogen-containing aromatic hydrocarbon according to claim 1, characterized in that: The reaction time is 10-50 minutes.

5. The method for preparing an N-terminated alkenyl nitrogen-containing aromatic hydrocarbon according to claim 4, characterized in that: The reaction time is 30 minutes.

6. The method for preparing an N-terminated alkenyl nitrogen-containing aromatic hydrocarbon according to claim 1, characterized in that: Dimethyl sulfoxide (DMSO) is used as both a solvent and a reagent in the reaction.

7. The method for preparing an N-terminated alkenyl nitrogen-containing aromatic hydrocarbon according to claim 1, characterized in that: The molar ratio of aromatic aldehydes or heteroaromatic aldehydes to nitrogen-containing heteroaromatic hydrocarbons is 1:2.

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