CN102161646A - Stilbene derivative with 1,3,4-oxadiazole and preparation method and application thereof - Google Patents

Abstract

The invention provides a stilbene derivative containing 1,3,4-oxadiazole, a preparation method and application thereof. The preparation method of the stilbene derivative containing 1,3,4-oxadiazole specifically includes four reaction steps: oxidation ring closure reaction, NBS bromination reaction, triethyl phosphite esterification reaction and Wittig- Honner reacted. The stilbene derivatives containing 1,3,4-oxadiazole disclosed by the present invention have relatively significant growth and development inhibitory activity on Lepidoptera insects such as beet armyworm and Trichoplusia, and are useful for the development of environmentally friendly and efficient new Pesticides have important application value.

Description

Stilbene derivatives containing 1,3,4-oxadiazole and its preparation method and application

technical field

The invention relates to the field of pesticide chemistry and fine chemicals, in particular to a stilbene derivative containing 1,3,4-oxadiazole, a preparation method and application thereof.

Background technique

1,3,4-Oxadiazole derivatives have a variety of biological activities: such as insecticidal, bactericidal, anticancer, anti-inflammatory and so on. The reason why such derivatives have so many biological activities mainly depends on the basic skeleton with oxadiazole ring in the molecule. 2,5-disubstituted 1,3,4-oxadiazoles exhibit a wide range of biological activities such as insecticidal, herbicidal, and bactericidal depending on the 2,5-position substituents. A large number of research results show that a certain Some 2,5-disubstituted 1,3,4-oxadiazole derivatives have good insect growth inhibitory activity. Foreign companies have successively developed pesticides containing 1,3,4-oxadiazole structure such as the herbicide oxadiazon and the insecticide metoxadiazone. This class of compounds has unique biological activities, which has aroused widespread interest and intensive research on them.

Stilbene compounds exist in a variety of plants, and their biological activities such as anticancer, antioxidation, antithrombotic, and free radical scavenging have been reported in recent years, so they are considered to be a class of natural products with good development prospects. Stilbene whitening agents not only have a significant protective and synergistic effect on baculoviruses, but also can significantly increase the sensitivity of parasites to viruses.

Although 1,3,4-oxadiazole derivatives have a variety of biological activities, their synthesis conditions are generally harsh, requiring higher temperatures, and corrosive dehydrating agents, etc., and post-treatment is more difficult. In addition, 1, The single active structural units of 3,4-oxadiazole and stilbene have a narrow application range and the effect is not obvious.

Contents of the invention

In view of the defects in the prior art, the object of the present invention is to provide stilbene derivatives containing 1,3,4-oxadiazole.

Containing stilbene derivatives of 1,3,4-oxadiazole, the specific structural formula is as follows:

Where Ar ₁ and Ar ₂ are phenyl, 4-trifluoromethylphenyl, 4-fluorophenyl, 4-chlorophenyl, 4-bromophenyl, 4-methoxyphenyl, 4-nitrobenzene Base, 4-dimethylaminophenyl, 3-trifluoromethylphenyl, 3-fluorophenyl, 3-chlorophenyl, 3-bromophenyl, 3-methoxyphenyl, 3-nitrobenzene Base, 2-trifluoromethylphenyl, 2-fluorophenyl, 2-chlorophenyl, 2-bromophenyl, 2-methoxyphenyl, 2-nitrophenyl, 2,4-dichloro Phenyl, 3,4-dichlorophenyl, 1-naphthyl or 9-anthracenyl; Ar ₁ and Ar ₂ are the same or different.

、（2）

、（3）

、（4）

、（5）

、（6）

、（7）

、（8）

、（9）

、（10）、（11）

、（12）

、（13）

、（14）

、（15）

、（16）、（17）、（18）

、（19）

、（20）

、（21）

、（22）

、（23）

、（24）

。The above-mentioned Ar ₁ and Ar ₂ have one of the following structures: (1)

,(2)

, (3)

, (4)

, (5)

, (6)

, (7)

,(8)

,(9)

, (10) , (11)

, (12)

, (13)

, (14)

, (15)

, (16) , (17) , (18)

, (19)

, (20)

,(twenty one)

,(twenty two)

,(twenty three)

,(twenty four)

.

Another object of the present invention is to provide a preparation method of stilbene derivatives containing 1,3,4-oxadiazole, which is specifically carried out according to the following chemical reaction steps:

(1) Formation of acylhydrazone and oxidative cyclization reaction

(2) Bromination reaction of N-bromosuccinimide

(3) Triethyl phosphite esterification reaction

(4) Wittig-Honner reaction

Containing 1,3, the preparation method of the stilbene derivative of 4-oxadiazole specifically comprises the following steps:

(1) Oxidative cyclization reaction

Dissolve equimolar aromatic aldehyde and p-toluyl hydrazide in ethanol, the volume molar ratio of ethanol and aromatic aldehyde and ethanol to p-toluyl hydrazide is 3 ~ 4ml/mmol, heat and stir to reflux 0.5 The reaction solution is obtained after ~2h; the reaction solution is cooled and filtered, and the filter cake is dried to obtain an intermediate; the intermediate is dissolved in ethanol, and chloramine T is added, and the intermediate reaction solution is obtained after heating, stirring and reflux for 3-5 hours, After ethanol is removed, the remaining solid is cooled and washed with distilled water and filtered for 3 to 5 times, and the filter cake is dried. The obtained filter cake is recrystallized with a mixture of distilled water and acetone at a volume ratio of 1:1 to 3 to obtain the recrystallized product A; The mol ratio of said intermediate and chloramine T is 1:3～7, and the volume molar ratio of ethanol and intermediate is 10～20ml/mmol;

(2) Bromination reaction of N-bromosuccinimide

Dissolve the above recrystallized product A and N-bromosuccinimide with a molar ratio of 1:1 to 1.5 in carbon tetrachloride, and then add a mass ratio of 0.01 to N-bromosuccinimide The initiator benzoyl peroxide of 0.02:1 is heated and stirred to reflux to obtain the reaction solution, and the reaction end point of the reaction solution is detected by thin-layer chromatography, and the remaining solid after removing carbon tetrachloride is washed with ethanol and filtered; the filter cake is dried After recrystallization with tetrahydrofuran and methanol mixed solution with a volume ratio of 1:1 ~ 5, the recrystallized product B is obtained; the volume molar ratio of the carbon tetrachloride and N-bromosuccinimide is 3 ~ 6ml/mmol ;

(3) Triethyl phosphite esterification reaction

Mix and dissolve the above-mentioned recrystallized product B with a molar ratio of 1:1.1~1.5 and oily liquid triethyl phosphite, stir and reflux at a temperature of 115~125°C for 3~6 hours, and remove excess phosphite in the reaction system under reduced pressure. After triethyl phosphite, add n-hexane to precipitate a solid product; the solid product is recrystallized with a mixture of tetrahydrofuran and n-hexane with a volume ratio of 1:1-4 to obtain recrystallized product C;

(4) Wittig-Honner reaction

Dissolving equimolar aromatic aldehydes and the recrystallized product C obtained in step (3) in N, N-dimethylformamide to obtain a solution; adding 15 to 30% by mass of An anhydrous ethanol solution of potassium tert-butoxide, stirred and reacted at 60-70°C for 5-9 hours to obtain a reaction solution, cooled and filtered the reaction solution; the obtained filter cake was made of dimethyl The final product obtained by recrystallization from a mixture of sulfoxide and ethanol, that is, a stilbene derivative containing 1,3,4-oxadiazole; the volume-to-mass ratio of the N,N-dimethylformamide to the recrystallized product C 10-15ml/g.

Another object of the present invention is the application of the stilbene derivatives containing 1,3,4-oxadiazole in inhibiting the growth and development activities of Lepidoptera insects such as beet armyworm and Trichoplusia spp.

Compared with prior art, the present invention has following advantage:

(1) The preparation conditions of the stilbene derivatives containing 1,3,4-oxadiazole of the present invention are mild, and the synthesis operation is simple;

(2) The stilbene derivatives containing 1,3,4-oxadiazole of the present invention contain both a 1,3,4-oxadiazole structure and a stilbene structure, and have significant inhibitory activity on insect growth and development, It has important application value for the development of environmentally friendly and efficient new insecticides.

Detailed ways

In order to better understand the present invention, the present invention will be further described below in conjunction with specific examples, but the protection scope of the present invention is not limited to the scope indicated by the examples.

The melting point and nuclear magnetic resonance data of the final product prepared in the examples were measured by RY-1 melting point instrument (Tianjin Analytical Instrument Factory) and BrukerAVANCE-400NMR nuclear magnetic resonance instrument (Bruker, Switzerland).

Example 1 Synthesis of 2-phenyl-5-(4-(3,4-dichlorostyryl)phenyl)-1,3,4-oxadiazole (I)

(I)

(1) Dissolve 30.0g (0.20mol) of p-toluylhydrazide in 700ml of absolute ethanol, add 21.2g (0.20mol) of benzaldehyde, heat and stir under reflux for 0.5h to obtain a reaction solution, cool and filter the reaction liquid, and dry the filter cake to obtain 42.0g of white solid; weigh 23.8g (0.10mol) of the white solid and dissolve it in 500ml of absolute ethanol, then add 85g (0.30mol) of chloramine T, heat and reflux and stir for 3h to obtain the intermediate reaction solution , the remaining solid after ethanol was evaporated was washed with distilled water and filtered 4 times, and the filter cake was dried, and the resulting dry filter cake was recrystallized with a mixed solution of distilled water and acetone with a volume ratio of 1:1 to obtain 15.75g 2-phenyl-5- (4-Benzyl)-1,3,4-oxadiazole, its yield: 66.7%. Melting point: 129°C. Proton NMR structural characterization data: 1H NMR (400 MHz, CDCl ₃ ) δ = 8.14 (d, J=7.5, 2H, C ₆ H _{5 2,} 6-H), 8.03 (d, J=7.9, 2H, C ₆ H ₄ 2,6-H), 7.65-7.45 (m, 3H, C ₆ H ₅ 3,4,5-H), 7.34 (d, J=7.9, 2H, C ₆ H ₄ 3,5- H), 2.44 (s, 3H, _CH3 );

(2) 13.0g (0.055mol) of 2-phenyl-5-(4-benzyl)-1,3,4-oxadiazole and 11.2g (0.063mol) of N-substituted Dissolve succinimide (NBS) in 200ml of carbon tetrachloride, then add 0.11g of benzoyl peroxide as an initiator, heat and stir under reflux, and detect the reaction end point of the reaction solution by TLC. After distilling off carbon tetrachloride, 15ml of ethanol was added to the remaining solid and filtered, and the filter cake was dried. The resulting dry filter cake was recrystallized with a mixed solution of tetrahydrofuran and methanol with a volume ratio of 1:3 to obtain the final product: 12.26g 2-phenyl-5-(4 -(bromomethyl)phenyl)-1,3,4-oxadiazole. Final product yield: 70.7%. Melting point: 166°C. Proton NMR structural characterization data: 1H NMR (400 MHz, CDCl ₃ ) δ 8.16 (d, J = 8.0 Hz, 2H, C ₆ H _{5 2,} 6-H), 8.13 (d, J = 8.8 Hz, 2H , C ₆ H ₄ 2,6-H), 7.75 (d, J = 8.2 Hz, 2H, C ₆ H ₄ 3,5-H), 7.62 -7.50 (m, 3H, C ₆ H ₅ 3,4, 5-H), 4.54 (s, 2H, _CH2Br );

(3) Dissolve 12.0g (0.038mol) of 2-phenyl-5-(4-(bromomethyl)phenyl)-1,3,4-oxadiazole prepared in step (2) in 7.9ml (0.046mol) triethyl phosphite, heated to 125°C, stirred and refluxed for 4 hours, evaporated the excess triethyl phosphite in the reaction system, then added 10ml of n-hexane to cool and precipitate the solid product, and the obtained solid product was obtained by volume 13.06 g of 4-(5-phenyl-1,3,4-oxadiazol-2-yl)benzylphosphonate was obtained by recrystallization from a mixture of tetrahydrofuran and n-hexane at a ratio of 1:2. Yield: 92.1%. Melting point: 118°C. Proton NMR structural characterization data: 1H NMR (400 MHz, CDCl ₃ ) δ 8.14 (d, J = 6.4 Hz, 2H, C ₆ H _{5 2,} 6-H), 8.10 (d, J = 7.9 Hz, 2H , C ₆ H ₄ 2,6-H), 7.60 -7.51 (m, 3H, C ₆ H ₅ 3,4, 5-H), 7.49 (d, J = 7.7 Hz, 2H, C ₆ H ₄ 3, 5-H), 4.06 (m, 4H, OCH ₂ ), 3.24 (d, J = 22.1 Hz, 2H, CH ₂ ), 1.27 (t, J = 7.0 Hz, 6H, CH ₃ );

(4) 1.0 g (2.69 mmol) of step (3) 4-(5-phenyl-1,3,4-oxadiazol-2-yl) benzyl phosphonate and 0.47 g (2.69 mmol) of 3 , 4-dichlorobenzaldehyde is dissolved in 15ml N, and obtains lysate in N-dimethylformamide, then in described lysate, dripping is the absolute ethanol solution 4ml of the potassium tert-butoxide of 20% by mass percentage, Stir the reaction at 60° C. for 5 h to obtain a reaction solution, cool and filter the reaction solution, and recrystallize the obtained filter cake with a mixture of dimethyl sulfoxide and ethanol at a volume ratio of 5:1 to obtain the final product. Yield: 92.3%. Melting point: 216°C. Proton NMR structural characterization data: 1H NMR (400 MHz, CDCl3) δ 8.15 (d, J = 6.9 Hz, 4H, C ₆ H ₅ C ₆ H _{4 2,} 6-H), 7.69 (d, J = 8.1 Hz, 2H, C ₆ H ₄ 3,5-H), 7.64 (d, J = 8.5 Hz, 1H, C ₆ H ₃ 6-H), 7.57-7.50 (m, 4H, C ₆ H ₃ 5-H , C ₆ H ₅ 3,4,5-H), 7.44 (s, 1H, C ₆ H ₃ 2-H), 7.27 (d, J = 16.3 Hz, 1H, CH=CH), 7.10 (d, J = 16.3 Hz, 1H, CH=CH).核磁共振碳谱结构表征数据：13C NMR (101 MHz， CDCl3) δ 164.62， 164.37， 140.07， 134.21， 134.15， 133.50， 131.78， 130.44， 129.73， 129.11， 127.46， 127.42， 127.36， 127.32， 126.98， 125.84， 123.92 , 123.30, conforming to the structural features.

Example 2 Synthesis of 2-phenyl-5-(4-(2,4-dichlorostyryl)phenyl)-1,3,4-oxadiazole (II)

(II)

Reaction steps (1), (2), (3) are the same as in Example 1, and the recrystallization product of step (3) gained is the same as that of Example 1;

(4) 1.0 g (2.69 mmol) of 4-(5-phenyl-1,3,4-oxadiazol-2-yl) benzyl phosphonate prepared in step (3) and 0.47 g ( 2.69mmol) 2,4-dichlorobenzaldehyde was dissolved in 10ml N,N-dimethylformamide to obtain a solution, then in the solution, dropwise added anhydrous potassium tert-butoxide with a mass percentage of 20%. 6ml of ethanol solution, stirred and reacted at 60°C for 5 h to obtain a reaction solution, cooled and filtered the reaction solution, and the resulting filter cake was recrystallized with a mixture of dimethyl sulfoxide and ethanol at a volume ratio of 7:1 to obtain the final product. Yield: 91.2%. Melting point: 213.8°C. Proton NMR structural characterization data: 1H NMR (400 MHz, CDCl ₃ ) δ 8.14 (d, J = 7.8 Hz, 4H, C ₆ H ₅ C ₆ H _{4 2,} 6-H), 7.65 (d, J = 8.1 Hz, 2H, C ₆ H ₄ 3,5-H), 7.63 (s, 1H, C ₆ H ₃ 3-H), 7.59-7.51 (m, 3H, C ₆ H ₅ 3,4,5-H ), 7.45 (d, J = 8.3 Hz, 1H, C ₆ H ₃ 6-H), 7.36

(d, J = 8.3 Hz, 1H, C ₆ H ₃ 5-H), 7.12 (s, 2H, CH=CH), carbon NMR structure characterization data: 13C NMR (101 MHz, CDCl ₃ ) δ 164.60, 164.35, 139.88, 136.88, 133.01, 131.86, 131.79, 130.72, 129.29, 129.11, 128.39, 128.34, 127.38, 127.22, 126.97, 125.89, 223.30 conform to the structure.

Example 3 Synthesis of 2-(2,4-dichlorophenyl)-5-(4-styrylphenyl)-1,3,4-oxadiazole (Ⅲ)

(Ⅲ)

(1) Dissolve 15.0g (0.10mol) of p-toluylhydrazide in 300ml of absolute ethanol, add 17.5g (0.10mol) of 2,4-dichlorobenzaldehyde, heat and stir under reflux for 1 hour to obtain a reaction solution, and cool And filter the reaction solution, dry the filter cake to obtain 29.5g white solid; weigh 29.0g (0.095mol) white solid and dissolve it in 500ml absolute ethanol, then add 136g (0.48mol) chloramine T, heat, stir and reflux for 5h The intermediate reaction solution was obtained, and the remaining solid was washed with distilled water and filtered 5 times after the ethanol was evaporated, and the obtained filter cake was dried, and the dried product was recrystallized with a mixed solution of distilled water and acetone with a volume ratio of 1:2 to obtain 15.59 g of 2- (2,4-Dichlorophenyl)-5-(4-benzyl)-1,3,4-oxadiazole. Yield: 53.9%. Melting point: 139°C. Proton NMR structural characterization data: 1H NMR (400 MHz, CDCl ₃ ) δ 8.16 (d, J = 8.0 Hz, 2H, C ₆ H _{5 2,} 6-H), 8.13 (d, J = 8.8 Hz, 2H , C ₆ H ₄ 2,6-H), 7.75 (d, J = 8.2 Hz, 2H, C ₆ H ₄ 3,5-H), 7.62-7.50 (m, 3H, C ₆ H ₅ 3,4, 5-H), 4.54 (s, 2H, CH2);

(2) 11.5g (0.038mol) of 2-(2,4-dichlorophenyl)-5-(4-benzyl)-1,3,4-oxadiazole and 7.7 g (0.043mol) N-generation succinimide (NBS) was dissolved in 150ml of carbon tetrachloride, then 0.07g of benzoyl peroxide was added as an initiator, heated and stirred to reflux, TLC detected the end point of the reaction, evaporated Carbon tetrachloride, 20ml of ethanol was added to the remaining solid and filtered, the filter cake was dried, and the resulting dry product was recrystallized with a mixed solution of tetrahydrofuran and methanol with a volume ratio of 1:2 to obtain 10.33g of 2-(2,4-di Chlorophenyl)-5-(4-(bromomethyl)phenyl)-1,3,4-oxadiazole, its yield: 71.4%. Melting point: 175°C. Proton NMR structural characterization data: 1H NMR (400 MHz, CDCl ₃ ) δ 8.12 (d, J = 8.0 Hz, 2H, C ₆ H _{4 2,} 6-H), 8.08 (d, J = 8.5 Hz, 1H , C ₆ H ₃ 6-H), 7.61 (s, 1H, C ₆ H ₃ 3-H), 7.57 (d, J = 8.0 Hz, 2H, C ₆ H ₄ 3,5-H), 7.43 (d , J = 8.5 Hz, 1H, C ₆ H ₃ 5-H), 4.54 (s, 2H, CH ₂ Br);

(3) 9.0g (0.024mol) of 2-(2,4-dichlorophenyl)-5-(4-(bromomethyl)phenyl)-1,3,4 prepared in step (2) -Oxadiazole was dissolved in 4.5ml (0.030mol) of triethyl phosphite, heated to 120°C, stirred and refluxed for 5 hours, after evaporating excess triethyl phosphite in the reaction system, adding 20ml of n-hexane to cool and precipitate Solid product, the resulting solid product was recrystallized from a mixture of tetrahydrofuran and n-hexane with a volume ratio of 1:3 to obtain 9.62g of 4-(5-(2,4-dichlorophenyl)-1,3,4-oxadiazole- 2-yl) benzyl phosphonate, its yield: 71.37%. Melting point: 120°C. Proton NMR structural characterization data: 1H NMR (400 MHz, CDCl ₃ ) δ = 8.08 (d, J=8.4, 3H, C ₆ H _{4 2,} 6-HC ₆ H ₃ 6-H), 7.60 (s, 1H, C ₆ H ₃ 3-H), 7.49 (d, J=8.4, 2H, C ₆ H ₄ 3,5-H), 7.43 (d, J=8.4, 1H, C ₆ H ₃ 5-H) , 4.06 (m, 4H, OCH ₂ ), 3.25 (d, J=22.1, 2H, CH2), 1.27 (t, J=7.0, 6H, CH ₃ );

(4) 1.0g (2.45mmol) of 4-(5-(2,4-dichlorophenyl)-1,3,4-oxadiazol-2-yl)benzyl obtained in step (3) Base phosphonate and 0.26g (2.45mmol) benzaldehyde were dissolved in 10ml N, N-dimethylformamide to obtain a dissolving solution, then in the said dissolving solution, dropwise adding mass percent of 30% potassium tert-butoxide 7ml of absolute ethanol solution, stirred and reacted at 70°C for 6 h to obtain a reaction solution, cooled and filtered the reaction solution, and the resulting filter cake was recrystallized with a mixed solution of dimethyl sulfoxide and ethanol with a volume ratio of 8:1 to obtain the final product Product, its yield: 89.5%. Melting point: 213.8°C. Proton NMR structural characterization data: 1H NMR (400 MHz, CDCl ₃ ) δ 8.12 (d, J = 8.2 Hz, 2H, C ₆ H _{4 2,} 6-H), 8.08 (d, J = 8.5 Hz, 1H , C ₆ H ₃ 6-H), 7.67 (d, J = 8.1 Hz, 2H, C ₆ H _{5 2,} 6-H), 7.61 (s, 1H, C ₆ H ₃ 3-H), 7.55 (d , J = 7.6 Hz, 2H, C ₆ H ₄ 3, 5-H), 7.43 (d, J = 8.6 Hz, 1H, C ₆ H ₃ 5-H), 7.39 (t, J = 8.1 Hz, 2H, C ₆ H ₅ 3,5-H), 7.31 (t, J = 7.3 Hz, 1H, C ₆ H ₅ 4-H), 7.26 (d, J = 16.3 Hz, 1H, CH=CH), 7.15 (d , J = 16.3 Hz, 1H, CH=CH), conforming to the structural characteristics.

Example 4 Synthesis of 2-(2,4-dichlorophenyl)-5-(4-(2,4-dichlorostyryl)phenyl)-1,3,4-oxadiazole (IV)

(Ⅳ)

Reaction steps (1), (2), (3) are the same as in Example 3, and the recrystallization product obtained in step (3) is the same as that in Example 3;

(4) 1.0g (2.45mmol) of 4-(5-(2,4-dichlorophenyl)-1,3,4-oxadiazol-2-yl)benzyl obtained in step (3) Base phosphonate and 0.79g (2.45mmol) 2,4-dichlorobenzaldehyde were dissolved in 15ml N,N-dimethylformamide to obtain a solution, and then added dropwise to the solution with a mass percentage of 15% Potassium tert-butoxide in absolute ethanol solution 8ml, stirred and reacted at 70°C for 7 h to obtain a reaction solution, cooled and filtered the reaction solution, and the obtained filter cake was mixed with dimethyl sulfoxide and ethanol with a volume ratio of 9:1 The mixture was recrystallized to obtain the final product. Yield: 85.9%. Melting point: 201.5°C. Proton NMR structural characterization data: 1H NMR (400 MHz, CDCl ₃ ) δ 8.14 (d, J = 8.1 Hz, 2H, C ₆ H _{4 2,} 6-H), 8.09 (d, J = 8.5 Hz, 1H , C ₆ H ₃ 6-H), 7.69 (d, J = 8.1 Hz, 2H, C ₆ H _{4 3,} 5-H), 7.64 (d, J = 8.5 Hz, 1H, C ₆ H ₃ 6-H ), 7.61 (s, 1H, C ₆ H ₃ 3-H), 7.56 (d, J = 16.3 Hz, 1H, CH=CH), 7.43 (d, J = 4.5 Hz, 2H, C ₆ H ₃ 3, 5-H), 7.09 (d, J = 16.3 Hz, 1H, CH=CH), carbon nuclear magnetic resonance spectrum structure characterization data: ¹³ C NMR (101 MHz, CDCl ₃ ) δ 164.97, 162.35, 140.37, 138.17, 134.23, 133.81, 133.41, 131.90, 131.27, 130.32, 129.74, 127.70, 127.51, 127.46, 127.31, 126.01, 122.89, 121.69, conform to the structural features.

Example 5 Synthesis of 2-(2,4-dichlorophenyl)-5-(4-(3,4-dichlorostyryl)phenyl)-1,3,4-oxadiazole (Ⅴ)

(V)

Reaction steps (1), (2), (3) are the same as in Example 3, and the recrystallization product obtained in step (3) is the same as that in Example 3;

(4) 1.0g (2.45mmol) of 4-(5-(2,4-dichlorophenyl)-1,3,4-oxadiazol-2-yl)benzyl obtained in step (3) Base phosphonate and 0.79g (2.45mmol) 3,4-dichlorobenzaldehyde were dissolved in 15ml N,N-dimethylformamide to obtain a solution, and then added dropwise to the solution with a mass percentage of 20% Potassium tert-butoxide in absolute ethanol solution 6ml, stirred and reacted at 65°C for 6.5 h to obtain a reaction solution, cooled and filtered the reaction solution, and the obtained filter cake was mixed with dimethyl sulfoxide and ethanol with a volume ratio of 6:1 The mixture was recrystallized to obtain the final product. Yield: 87.3%. Melting point: 253°C. Proton NMR structural characterization data: ¹ H NMR (400 MHz, CDCl ₃ ) δ 8.15 (d, J = 7.9 Hz, 2H, C ₆ H _{4 2,} 6-H), 8.09 (d, J = 8.5 Hz, 1H, C ₆ H ₃ 6-H), 7.66 (d, J = 8.3 Hz, 1H, C ₆ H ₄ 3, 5-H), 7.63 (d, J = 7.1 Hz, 1H, C ₆ H ₃ 6- H), 7.52 (s, 1H, C ₆ H ₃ 3-H), 7.46 (d, J = 7.5 Hz, 1H, C ₆ H ₃ 5-H), 7.43 (s, 1H, C ₆ H ₃ 2- H), 7.37 (d, J = 8.9 Hz, 1H, C ₆ H ₃ 5-H), 7.13 (s, 2H, CH=CH), consistent with structural features.

Example 6 2-(4-(2-(Anthracene-9-yl)vinyl)phenyl)-5-(2,4-dichlorophenyl)-1,3,4-oxadiazole (Ⅵ) Synthesis

(VI)

Reaction steps (1), (2), (3) are the same as in Example 3, and the recrystallization product obtained in step (3) is the same as that in Example 3;

(4) 1.0g (2.45mmol) of 4-(5-(2,4-dichlorophenyl)-1,3,4-oxadiazol-2-yl)benzyl obtained in step (3) Base phosphonate and 0.51g (2.45mmol) 9-anthracene formaldehyde were dissolved in 15ml N,N-dimethylformamide to obtain a solution, and then 25% tert-butanol was added dropwise to the solution Potassium in absolute ethanol solution 5ml, stirred and reacted at 70°C for 7 h to obtain a reaction solution, cooled and filtered the reaction solution, and the obtained filter cake was recrystallized with a mixed solution of dimethyl sulfoxide and ethanol with a volume ratio of 5:1 get the final product. Yield: 88.5%. Proton NMR structural characterization data: ¹ H NMR (400 MHz, CDCl ₃ ) δ 8.45 (s, 1H, anthracen-H), 8.35 (d, J = 10.0 Hz, 2H, anthracen-H), 8.23 (d, J = 8.3 Hz, 2H, C ₆ H _{4 2,} 6-H), 8.12 (d, J = 8.2 Hz, 1H, C ₆ H ₃ 6-H), 8.10 (d, J = 16.0 Hz, 1H, CH =CH), 8.04 (d, J = 9.8 Hz, 2H, C ₁₄ H _{9 4,} 5-H), 7.84 (d, J = 8.3 Hz, 2H, C ₆ H _{4 3,} 5-H), 7.63 ( s, 1H, C ₆ H ₃ 2-H), 7.53-7.48 (m, 4H, anthracen-H), 7.45 (d, J = 8.5 Hz, 1H, C ₆ H ₃ 5-H), 7.03 (d, J = 16.5 Hz, 1H, CH=CH), consistent with the structural features.

Example 7 Synthesis of 2-(3,4-dichlorophenyl)-5-(4-styrylphenyl)-1,3,4-oxadiazole (VII)

(VII)

(1) Dissolve 15.0g (0.10mol) of p-toluylhydrazide in 400ml of absolute ethanol, add 17.5g (0.10mol) of 3,4-dichlorobenzaldehyde, heat, stir and reflux for 1.5h to obtain a reaction solution , cooled and filtered the reaction solution, dried the filter cake to obtain 29.5g of white solid; weighed 28.0g (0.091mol) of white solid and dissolved it in 500ml of absolute ethanol, added 155g (0.55mol) of chloramine T, heated and stirred under reflux reaction 3.5h to obtain the intermediate reaction solution, the solid after distilling off the ethanol was washed with distilled water and filtered 3 times, and the filter cake was dried. The resulting dry filter cake was recrystallized with a mixed solution of distilled water and acetone with a volume ratio of 1:3 to obtain 12.68 g of 2- (3,4-Dichlorophenyl)-5-(4-benzyl)-1,3,4-oxadiazole, its yield: 50.2%. Melting point: 158.7°C. Proton NMR structural characterization data: ¹ H NMR (400 MHz, CDCl ₃ ) δ = 8.20 (s, 1H, C ₆ H ₃ 2-H), 8.01 (d, J=7.9, 2H, C ₆ H ₄ 2 , 6-H), 7.97 (d, J=8.4, 1H, C ₆ H ₃ 6-H), 7.61 (d, J=8.4, 1H, C ₆ H ₃ 5-H), 7.34 (d, J= 7.8, 2H, _{C6H43 ,} 5-H), 2.44 (s, 3H, _CH3 );

(2) Mix 8.0g (0.025mol) of 2-(3,4-dichlorophenyl)-5-(4-benzyl)-1,3,4-oxadiazole and 5.4 g (0.030mol) N-generation succinimide (NBS) was dissolved in 120ml of carbon tetrachloride, and then 0.05g of benzoyl peroxide was added as an initiator, heated and stirred under reflux, and the end point of the reaction solution was detected by TLC. After the carbon tetrachloride was evaporated, the remaining solid was washed with 25ml of ethanol and filtered. After the filter cake was dried, it was recrystallized with a mixture of tetrahydrofuran and methanol at a volume ratio of 1:5 to obtain 9.21g of 2-(3,4-dichlorobenzene base)-5-(4-(bromomethyl)phenyl)-1,3,4-oxadiazole. Yield: 91.5%. Melting point: 185°C. Proton NMR structural characterization data: ¹ H NMR (400 MHz, CDCl ₃ ) δ 8.21 (s, 1H, C ₆ H ₃ 2-H), 8.11 (d, J = 8.0 Hz, 2H, C ₆ H ₄ 2 , 6-H), 7.98 (d, J = 8.4 Hz, 1H, C ₆ H ₃ 6-H), 7.62 (d, J = 8.4 Hz, 1H, C ₆ H ₃ 5-H), 7.57 (d, J = 7.9 Hz, 2H, _{C6H43 , 5} -H), 4.54 (s, 2H, _CH2Br );

(3) 9.0g (0.024mol) of 2-(3,4-dichlorophenyl)-5-(4-(bromomethyl)phenyl)-1,3,4 prepared in step (2) -Oxadiazole was dissolved in 5.4ml (0.036mol) of triethyl phosphite, heated to 120°C, stirred and refluxed for 6 hours, after depressurizing to remove excess triethyl phosphite in the reaction system, add 40ml of n-hexane to cool A solid product was precipitated, and the resulting solid product was recrystallized from a mixture of tetrahydrofuran and n-hexane with a volume ratio of 1:4 to obtain 8.69 g of 4-(5-(3,4-dichlorophenyl)-1,3,4-oxadiazole -2-yl) benzyl phosphonate. Yield: 90.3%. Melting point: 124-125°C. Proton NMR structural characterization data: ¹ H NMR (400 MHz, CDCl ₃ ) δ 8.22 (s, 1H, C ₆ H ₃ 2-H), 8.09 (d, J = 7.8 Hz, 2H, C ₆ H ₄ 2 , 6-H), 7.99 (d, J = 8.4 Hz, 1H, C ₆ H ₃ 6-H), 7.63 (d, J = 8.3 Hz, 1H, C ₆ H ₃ 5-H), 7.50 (d, J = 7.6 Hz, 2H, C ₆ H ₄ 3, 5-H), 4.06 (m, 4H, OCH ₂ ), 3.25 (d, J = 22.1 Hz, 2H, CH ₂ ), 1.27 (t, J = 7.0 Hz, 6H, CH ₃ );

(4) 1.0g (2.45mmol) of 4-(5-(3,4-dichlorophenyl)-1,3,4-oxadiazol-2-yl)benzyl obtained in step (3) Base phosphonate and 0.26g (2.45mmol) benzaldehyde were dissolved in 15ml N, N-dimethylformamide to obtain a dissolving solution, and then in the dissolving solution, dropwise adding mass percent of 25% potassium tert-butoxide 5ml of absolute ethanol solution, stirred and reacted at 65°C for 6 h to obtain a reaction solution, cooled and filtered the reaction solution, and the obtained filter cake was recrystallized with a mixed solution of dimethyl sulfoxide and ethanol with a volume ratio of 6:1 to obtain the final product product. Yield: 90.3%. Melting point: 215-216°C. Proton NMR structural characterization data: ¹ H NMR (400 MHz, CDCl ₃ ) δ 8.24 (s, 1H, C ₆ H ₃ 2-H), 8.12 (d, J = 8.0 Hz, 2H, C ₆ H ₄ 2 , 6-H), 8.00 (d, J = 8.4 Hz, 1H, C ₆ H ₃ 6-H), 7.68 (d, J = 8.1 Hz, 2H, C ₆ H _{5 2,} 6-H), 7.63 ( d, J = 8.4 Hz, 1H, C ₆ H ₃ 5-H), 7.56 (d, J = 7.7 Hz, 2H, C ₆ H ₄ 3, 5-H), 7.40 (t, J = 7.4 Hz, 2H , C ₆ H ₅ 3,5-H), 7.31 (t, J = 7.3 Hz, 1H, C ₆ H ₅ 4-H), 7.26 (d, J = 16.2 Hz, 1H, CH=CH), 7.15 ( d, J = 16.3 Hz, 1H, CH=CH), consistent with the structural features.

Example 8 Synthesis of 2-(3,4-dichlorophenyl)-5-(4-(3,4-dichlorostyryl)phenyl)-1,3,4-oxadiazole (Ⅷ)

(Ⅷ)

Reaction steps (1), (2), (3) are the same as in Example 7, and the recrystallization product obtained in step (3) is the same as in Example 7;

(4) 1.0g (2.45mmol) of 4-(5-(3,4-dichlorophenyl)-1,3,4-oxadiazol-2-yl)benzyl obtained in step (3) Phosphonic acid ester and 0.79g (2.45mmol) 3,4-dichlorobenzaldehyde were dissolved in 15ml N,N-dimethylformamide to obtain a solution, and then added dropwise to the solution with a mass percentage of 30% Potassium tert-butoxide in absolute ethanol solution 4ml, stirred and reacted at 70°C for 8 h to obtain a reaction solution, cooled and filtered the reaction solution, and the obtained filter cake was mixed with dimethyl sulfoxide and ethanol with a volume ratio of 4:1 The mixture was recrystallized to obtain the final product. Yield: 85.8%. Melting point: 277°C. Proton NMR structural characterization data: ¹ H NMR (400 MHz, CDCl ₃ ) δ 8.24 (s, 1H, C ₆ H ₃ 2-H), 8.14 (d, J = 8.3 Hz, 2H, C ₆ H ₄ 2 , 6-H), 8.01 (d, J = 8.7 Hz, 1H, C ₆ H ₃₆ -H), 7.67 (d, J = 8.3 Hz, 2H, C ₆ H _{4 3,} 5-H), 7.63 (d , J = 4.4 Hz, 1H, C ₆ H ₃ 6-H), 7.52 (s, 1H, C ₆ H ₃ 2-H), 7.46 (d, J = 8.3 Hz, 1H, C ₆ H ₃ 5-H ), 7.37 (d, J = 8.1 Hz, 1H, C ₆ H ₃ 5-H), 7.14 (s, 2H, CH=CH), consistent with the structural features.

Example 9 Synthesis of 2-(3,4-dichlorophenyl)-5-(4-(2,4-dichlorostyryl)phenyl)-1,3,4-oxadiazole (IX)

(Ⅸ)

Reaction steps (1), (2), (3) are the same as in Example 7, and the recrystallization product obtained in step (3) is the same as in Example 7;

(4) 1.0g (2.45mmol) of 4-(5-(3,4-dichlorophenyl)-1,3,4-oxadiazol-2-yl)benzyl obtained in step (3) Phosphonic acid ester and 0.79g (2.45mmol) 2,4-dichlorobenzaldehyde were dissolved in 15ml N,N-dimethylformamide to obtain a solution, and then added dropwise to the solution with a mass percentage of 30% Potassium tert-butoxide in absolute ethanol solution 4ml, stirred and reacted at 70°C for 8 h to obtain a reaction solution, cooled and filtered the reaction solution, and the obtained filter cake was mixed with dimethyl sulfoxide and ethanol with a volume ratio of 7:1 The mixture was recrystallized to obtain the final product. Yield: 83.5%. Melting point: 221°C. Proton NMR structural characterization data: ¹ H NMR (400 MHz, CDCl ₃ ) δ 8.24 (s, 1H, C ₆ H ₃ 2-H), 8.14 (d, J = 8.1 Hz, 2H, C ₆ H ₄ 2 , 6-H), 8.00 (d, J = 7.9 Hz, 1H, C ₆ H ₃ 6-H), 7.70 (d, J = 8.1 Hz, 2H, C ₆ H _{4 3,} 5-H), 7.65 ( d, J = 3.6 Hz, 1H, C ₆ H ₃ 6-H), 7.63 (d, J = 3.3 Hz, 1H, C ₆ H ₃ 5-H), 7.57 (d, J = 16.3 Hz, 1H, C ₆ H ₃ 5-H), 7.44 (s, 1H, C ₆ H ₃ 3-H), 7.11 (d, J = 16.5 Hz, 2H, CH=CH), consistent with structural features.

Example 10 2-(4-(2-(Anthracene-9-yl)vinyl)phenyl)-5-(3,4-dichlorophenyl)-1,3,4-oxadiazole (X) Synthesis

(X)

Reaction steps (1), (2), (3) are the same as in Example 7, and the recrystallization product obtained in step (3) is the same as in Example 7;

(4) 1.0g (2.45mmol) of 4-(5-(3,4-dichlorophenyl)-1,3,4-oxadiazol-2-yl)benzyl obtained in step (3) Phosphonic acid ester and 0.51g (2.45mmol) 9-anthracene formaldehyde were dissolved in 15ml N,N-dimethylformamide to obtain a solution, and then 30% tert-butanol was added dropwise to the solution Potassium in absolute ethanol solution 4ml, stirred and reacted at 70°C for 8 h to obtain a reaction solution, cooled and filtered the reaction solution, and the resulting filter cake was recrystallized with a mixed solution of dimethyl sulfoxide and ethanol with a volume ratio of 6:1 get the final product. Yield: 89.2%. Proton NMR structural characterization data: ¹ H NMR (400 MHz, CDCl ₃ ) δ 8.45 (s, 1H, anthracen-H), 8.35 (d, J = 9.9 Hz, 2H, anthracen-H), 8.27 (s, 1H, C ₆ H ₃ 1-H), 8.22 (d, J = 8.3 Hz, 2H, C ₆ H _{4 2} , 6-H), 8.10 (d, J = 16.6 Hz, 1H, CH=CH), 8.0 (d, J = 8.0 Hz, 1H, C ₆ H ₃ 6-H), 8.03 (d, J = 6.5 Hz, 1H), 7.84 (d, J = 8.3 Hz, 2H, C ₆ H _{4 3} , 5- H), 7.65 (d, J = 8.0 Hz, 1H, C ₆ H ₃ 5-H), 7.60-7.45 (m, 4H, anthracen-H), 7.04 (d, J = 16.6 Hz, 1H, CH=CH ), conforming to the structural features.

Example 11 Synthesis of 2-(anthracene-9-yl)-5-(4-styrylphenyl)-1,3,4-oxadiazole (XI)

(Ⅺ)

(1) Dissolve 15.0g (0.10mol) of p-toluylhydrazide in 300ml of absolute ethanol, add 20.6g (0.10mol) of 9-anthracene formaldehyde, heat and stir under reflux for 2 hours to obtain a reaction solution, cool and filter the Reaction solution, dry the filter cake to obtain 33.3g white solid; weigh 30.0g (0.088mol) white solid and dissolve it in 500ml of absolute ethanol, add 173.5g (0.616mol) chloramine T, heat and reflux and stir for 5h to obtain the intermediate reaction After distilling off ethanol, the remaining solid was washed with distilled water and filtered three times, and the filter cake was dried. The resulting dry filter cake was recrystallized with a mixture of distilled water and acetone at a volume ratio of 1:4 to obtain 20.5 g of 2-(anthracene-9 -yl)-5-(4-benzyl)-1,3,4-oxadiazole, its yield: 67.1%. Proton NMR structural characterization data: ¹ H NMR (400 MHz, CDCl ₃ ) δ 8.67 (s, 1H, anthracen-H), 8.08 (d, J = 8.2 Hz, 2H, C ₆ H ₄ 2,6-H ), 8.10-8.05 (m, J = 9.3 Hz, 4H, anthracen-H), 7.58 -7.50 (m, 4H, anthracen-H), 7.35 (d, J = 8.0 Hz, 1H, C ₆ H ₄ 3, 5-H), 2.45 (s, 3H, _CH3 );

(2) Mix 8.8g (0.026mol) of 2-(anthracene-9-yl)-5-(4-benzyl)-1,3,4-oxadiazole and 9.3g (0.052mol) ) N-generation succinimide (NBS) was dissolved in 300ml of carbon tetrachloride, then 0.45g of benzoyl peroxide was added as an initiator, heated and stirred to reflux, TLC was used to detect the reaction end point of the reaction solution, and the tetrachloride was evaporated After carbonization, the remaining solid was washed with 30ml of ethanol and filtered, and after the filter cake was dried, it was recrystallized with a mixed solution of tetrahydrofuran and methanol with a volume ratio of 1:5 to obtain 8.34g 2-(Anthracen-9-yl)-5-(4 -(bromomethyl)phenyl)-1,3,4-oxadiazole. Yield: 77.5%;

(3) 8.15g (0.020mol) of 2-(anthracene-9-yl)-5-(4-(bromomethyl)phenyl)-1,3,4-oxadioxine obtained in step (2) Dissolve azole in 4.3ml (0.028mol) of triethyl phosphite, heat to 120°C, stir and reflux for 3 hours, evaporate excess triethyl phosphite in the reaction system, then add 35ml of n-hexane to cool and precipitate a solid product, The resulting solid product was recrystallized from a mixture of tetrahydrofuran and n-hexane with a volume ratio of 1:1 to obtain 7.26 g of 4-(5-(anthracene-9-yl)-1,3,4-oxadiazol-2-yl)benzene Methylphosphonate. Yield: 77.0%;

(4) 0.90g (1.91mmol) of 4-(5-(anthracene-9-yl)-1,3,4-oxadiazol-2-yl)benzylphosphonic acid prepared in step (3) Esters and 0.20g (1.91mmol) benzaldehyde are dissolved in 13ml N, and in N-dimethylformamide, obtain dissolving solution, then dropwise in described dissolving solution, be the dehydrated alcohol of the potassium tert-butoxide of 20% Solution 8ml, stirred and reacted at 70°C for 5 h to obtain a reaction solution, cooled and filtered the reaction solution, and the obtained filter cake was recrystallized with a mixed solution of dimethyl sulfoxide and ethanol with a volume ratio of 10:1 to obtain the final product. Yield: 72.8%. Proton NMR structural characterization data: ¹ H NMR (400 MHz, CDCl ₃ ) δ 8.70 (s, 1H, anthracen-H), 8.19 (d, J = 8.2 Hz, 2H, C ₆ H ₄ -H), 8.14 -7.99 (m, 4H, _{anthracen -} H), 7.69 (d, J = 8.3 Hz, 2H, _C6H4 -H), 7.60 -7.52 (m, 6H, anthracen- _HCC6H52 , 6- H), 7.39 (t, J = 7.5 Hz, 2H, C ₆ H ₅ 3, 5-H), 7.30 (t, J = 7.5 Hz, 1H, C ₆ H ₅ 4-H), 7.26 (d, J = 16.4 Hz, 2H, CH=CH), 7.16 (d, J = 16.3 Hz, 2H, CH=CH), carbon NMR structure characterization data: ¹³ C NMR (101 MHz, CDCl ₃ ) δ 165.72, 163.00, 140.97, 136.72, 131.48, 131.17, 131.06, 128.83, 128.79, 128.32, 127.76, 127.49, 127.42, 127.14, 126.82, 125.74, 125.12, 122.61, conform to the structural features.

Example 12 Synthesis of 2-(anthracene-9-yl)-5-(4-(4-fluorostyryl)phenyl)-1,3,4-oxadiazole (XII)

                          

(Ⅻ)

Reaction steps (1), (2), (3) are the same as in Example 11, and the recrystallized product obtained in step (3) is the same as that in Example 11;

(4) 0.9g (1.91mmol) of 4-(5-(anthracene-9-yl)-1,3,4-oxadiazol-2-yl)benzylphosphonic acid prepared in step (3) Esters and 0.24g (1.91mmol) 4-fluorobenzaldehyde were dissolved in 15ml N,N-dimethylformamide to obtain a solution, and then 8ml of anhydrous ethanol solution of 15% potassium tert-butoxide was added dropwise, Stir the reaction at 70° C. for 8 h to obtain a reaction solution, cool and filter the reaction solution, and recrystallize the resulting filter cake with a mixture of dimethyl sulfoxide and ethanol at a volume ratio of 5:1 to obtain the final product. Yield: 84.1%. Proton NMR structural characterization data: ¹ H NMR (400 MHz, CDCl ₃ ) δ 8.70 (s, 1H, anthracen-H), 8.19 (d, J = 8.2 Hz, 2H, C ₆ H ₄ 2,6-H ), 8.14 – 8.01 (m, 4H, anthracen-H), 7.67 (d, J = 8.2 Hz, 2H, C ₆ H ₄ 3, 5-H), 7.60 – 7.47 (m, 6H, anthracen-H C ₆ H ₄ -2,6-H), 7.22 (d, J = 16.3 Hz, 1H, CH=CH), 7.08 (t, J = 8.4 Hz 2H, C ₆ H ₄ 3,5-H), 7.07 (d , J = 16.1 Hz, 1H, CH=CH), carbon NMR spectrum structure characterization data: ¹³ C NMR (101 MHz, CDCl ₃ ) δ 165.68, 163.01, 140.80, 132.92, 131.49, 131.06, 129.91, 128.79, 128.41, 128.33, 127.76, 127.52, 127.22, 127.07, 125.74, 125.11, 122.66, 117.28, 115.94, 115.72, conform to the structural features.

Example 13 Synthesis of 2-(anthracene-9-yl)-5-(4-(4-chlorostyryl)phenyl)-1,3,4-oxadiazole (a)

                          

(a)

Reaction steps (1), (2), (3) are the same as in Example 11, and the recrystallized product obtained in step (3) is the same as that in Example 11;

(4) 0.9g (1.91mmol) of 4-(5-(anthracene-9-yl)-1,3,4-oxadiazol-2-yl)benzylphosphonate obtained in step (3) and 0.31 g (1.91mmol) 4-chlorobenzaldehyde was dissolved in 15ml N,N-dimethylformamide to obtain a solution, then in the solution, dropwise added dehydrated alcohol with 25% potassium tert-butoxide by mass Solution 6ml, stirred and reacted at 70°C for 8 h to obtain a reaction solution, cooled and filtered the reaction solution, and the obtained filter cake was recrystallized with a mixture of dimethyl sulfoxide and ethanol at a volume ratio of 6:1 to obtain the final product. Yield: 87.8%. Proton NMR structural characterization data: ¹ H NMR (400 MHz, CDCl ₃ ) δ 8.71 (s, 1H, anthracen-H), 8.19 (d, J = 8.2 Hz, 2H, C ₆ H ₄ 2,6-H ), 8.14 – 8.01 (m, 4H, anthracen-H), 7.68 (d, J = 8.2 Hz, 2H, C ₆ H ₄ 3, 5-H), 7.61 – 7.52 (m, 4H, anthracen-H), 7.48 (d, J = 8.4 Hz, 2H, C ₆ H _{4 2,} 6-H), 7.36 (d, J = 8.4 Hz, 2H, C ₆ H ₄ 3, 5-H), 7.20 (d, J = 16.3 Hz, 1H, CH=CH), 7.13 (d, J = 16.3 Hz, 1H, CH=CH), H NMR structural characterization data: ¹³ C NMR (101 MHz, CDCl ₃ ) δ 165.65, 163.04, 140.60 , 135.24, 133.95, 131.51, 131.47, 131.06, 129.79, 129.02, 128.80, 128.01, 127.96, 127.77, 127.53, 127.18, 125.75, 125.18, 4, 122. conform to the structure.

Example 14 Synthesis of 2-(anthracene-9-yl)-5-(4-(4-bromostyryl)phenyl)-1,3,4-oxadiazole (b)

(b)

Reaction steps (1), (2), (3) are the same as in Example 11, and the recrystallized product obtained in step (3) is the same as that in Example 11;

(4) 0.9g (1.91mmol) of 4-(5-(anthracene-9-yl)-1,3,4-oxadiazol-2-yl)benzylphosphonate obtained in step (3) and 0.35 g (1.91mmol) 4-bromobenzaldehyde was dissolved in 15ml N,N-dimethylformamide to obtain a solution, then in the solution, dropwise added dehydrated alcohol with 20% potassium tert-butoxide by mass percentage Solution 7ml, stirred and reacted at 70°C for 6 h to obtain a reaction solution, cooled and filtered the reaction solution, and the resulting filter cake was recrystallized with a mixture of dimethyl sulfoxide and ethanol at a volume ratio of 5:1 to obtain the final product. Yield: 80.9%. Proton NMR structural characterization data: ¹ H NMR (400 MHz, CDCl ₃ ) δ 8.71 (s, 1H, anthracen-H), 8.19 (d, J = 8.2 Hz, 2H, C ₆ H ₄ 2,6-H ), 8.13-8.04 (m, 4H, anthracen-H), 7.68 (d, J = 8.2 Hz, 2H, C ₆ H ₄ 3,5-H), 7.60 – 7.53 (m, 4H, anthracen-H), 7.51 (d, J = 8.4 Hz, 2H, C ₆ H _{4 2,} 6-H), 7.42 (d, J = 8.4 Hz, 2H, C ₆ H ₄ 3, 5-H), 7.19 (d, J = 16.5 Hz, 1H, CH=CH), 7.14 (d, J = 16.5 Hz, 1H, CH=CH), consistent with the structural features.

Example 15 Synthesis of 2-(anthracen-9-yl)-5-(4-(4-nitrostyryl)phenyl)-1,3,4-oxadiazole (c)

(c)

Reaction steps (1), (2), (3) are the same as in Example 11, and the recrystallized product obtained in step (3) is the same as that in Example 11;

(4) 0.9g (1.91mmol) of 4-(5-(anthracene-9-yl)-1,3,4-oxadiazol-2-yl)benzylphosphonic acid prepared in step (3) Esters and 0.20g (1.91mmol) 4-nitrobenzaldehyde were dissolved in 15ml N,N-dimethylformamide to obtain a solution, then in the solution, dropwise added potassium tert-butoxide with a mass percentage of 15% 8ml of absolute ethanol solution, stirred and reacted at 60°C for 8 h to obtain a reaction solution, cooled and filtered the reaction solution, and the resulting filter cake was recrystallized with a mixed solution of dimethyl sulfoxide and ethanol with a volume ratio of 8:1 to obtain end product. Yield: 78.2%. Proton NMR structural characterization data: ¹ H NMR (400 MHz, CDCl ₃ ) δ 8.72 (s, 1H, anthracen-H), 8.25 (d, J = 8.6 Hz, 2H, C ₆ H ₄ 3,5-H ), 8.23 (d, J = 8.2 Hz, 2H, C ₆ H ₄ 2, 6-), 8.15 – 8.03 (m, 4H, anthracen-H), 7.73 (d, J = 8.2 Hz, 2H, C ₆ H ₄ 2, 6-H), 7.68 (d, J = 8.6 Hz, 2H, C ₆ H ₄ 2, 6-H), 7.61 – 7.53 (m, 4H, anthracen-H), 7.33 (d, J = 16.5 Hz, 1H, CH=CH), 7.28 (d, J = 16.2 Hz, 1H, CH=CH), consistent with the structural features.

Example 16 Synthesis of 2-(anthracene-9-yl)-5-(4-(4-methylaminostyryl)phenyl)-1,3,4-oxadiazole (d)

(d)

Reaction steps (1), (2), (3) are the same as in Example 11, and the recrystallized product obtained in step (3) is the same as that in Example 11;

(4) 0.9g (1.91mmol) 4-(5-(anthracen-9-yl)-1,3,4-oxadiazol-2-yl) benzyl phosphonate and 0.28g (1.91mmol) 4-Methylaminobenzaldehyde is dissolved in 15ml N, and obtains solution in N-dimethylformamide, then in described solution, dripping is the dehydrated ethanol solution 4ml of the potassium tert-butoxide of 30% by mass percentage, in Stir and react at 70°C for 7 h to obtain a reaction solution, cool and filter the reaction solution, and recrystallize the obtained filter cake with a mixture of dimethyl sulfoxide and ethanol at a volume ratio of 7:1 to obtain the final product. Yield: 75.6%. Proton NMR structural characterization data: ¹ H NMR (400 MHz, CDCl ₃ ) δ 8.70 (s, 1H, anthracen-H), 8.15 (d, J = 8.2 Hz, 2H, C ₆ H ₄ 2,6-H ), 8.17-8.05 (m, 4H, anthracen-H), 7.64 (d, J = 8.2 Hz, 2H, C ₆ H _{4 3} , 5-H), 7.60 – 7.52 (m, 4H, anthracen-H), 7.46 (d, J = 8.4 Hz, 2H, C ₆ H _{4 2,} 6-H), 7.20 (d, J = 16.2 Hz, 1H, CH=CH), 6.97 (d, J = 16.2 Hz, 1H, CH =CH), 6.76 (d, J = 8.4 Hz, 2H, C ₆ H ₄ 3, 5-H), 3.02 (s, 6H, CH ₃ ), consistent with the structural features.

Example 17 Synthesis of 2-(anthracene-9-yl)-5-(4-(4-methoxystyryl)phenyl)-1,3,4-oxadiazole (e)

(e)

Reaction steps (1), (2), (3) are the same as in Example 11, and the recrystallized product obtained in step (3) is the same as that in Example 11;

(4) 0.9g (1.91mmol) 4-(5-(anthracen-9-yl)-1,3,4-oxadiazol-2-yl) benzyl phosphonate and 0.26g (1.91mmol) 4-Methylaminobenzaldehyde is dissolved in 15ml N, and obtains solution in N-dimethylformamide, then in described solution, dripping is the dehydrated ethanol solution 6ml of 25% potassium tert-butoxide in the described solution, in Stir the reaction at 65°C for 7 h to obtain a reaction liquid, cool and filter the reaction liquid, and recrystallize the obtained filter cake with a mixture of dimethyl sulfoxide and ethanol at a volume ratio of 5:1 to obtain the final product. Yield: 71.2%. Proton NMR structural characterization data: ¹ H NMR (400 MHz, CDCl ₃ ) δ 8.70 (s, 1H, anthracen-H), 8.17 (d, J = 8.2 Hz, 2H, C ₆ H ₄ 2,6-H ), 8.12-8.04 (m, 4H, anthracen-H), 7.65 (d, J = 8.2 Hz, 2H, C ₆ H _{4 3} , 5-H), 7.60 – 7.52 (m, 4H, anthracen-H), 7.50 (d, J = 8.5 Hz, 2H, C ₆ H _{4 2,} 6-H), 7.21 (d, J = 16.3 Hz, 1H, CH=CH), 7.02 (d, J = 16.3 Hz, 1H, CH =CH), 6.92 (d, J = 8.5 Hz, 2H, C ₆ H ₄ 3, 5-H), 3.84 (s, 3H, CH ₃ ), characterization data of carbon NMR spectrum: ¹³ C NMR (101 MHz ， CDCl ₃ ) δ 165.79， 162.92， 159.86， 141.37， 131.48， 131.45， 131.06， 130.73， 129.52， 128.78， 128.13， 127.74， 127.47， 126.84， 125.74， 125.27， 125.14， 122.15， 117.35， 114.29， 55.37，符合结构特征.

Example 18 Synthesis of 2-(anthracene-9-yl)-5-(4-(3,4-dichlorostyryl)phenyl)-1,3,4-oxadiazole (f)

(f)

Reaction steps (1), (2), (3) are with embodiment 11, and the recrystallization product of step (3) gained is identical with embodiment 11;

(4) 0.9g (1.91mmol) 4-(5-(anthracen-9-yl)-1,3,4-oxadiazol-2-yl) benzyl phosphonate and 0.34g (1.91mmol) 4-Methylaminobenzaldehyde is dissolved in 15ml N, and obtains solution in N-dimethylformamide, then in described solution, dripping is the dehydrated ethanol solution 4ml of the potassium tert-butoxide of 30% by mass percentage, in Stir the reaction at 70°C for 6 h, cool and filter the reaction solution, and recrystallize the resulting filter cake with a mixture of dimethyl sulfoxide and ethanol at a volume ratio of 6:1 to obtain the final product. Yield: 89.5%. Proton NMR structural characterization data: ¹ H NMR (400 MHz, CDCl ₃ ) δ 8.71 (s, 1H, anthracen-H), 8.20 (d, J = 8.2 Hz, 2H, C ₆ H ₄ 2,6-H ), 8.15 – 8.02 (m, 4H, anthracen-H), 7.68 (d, J = 8.3 Hz, 2H, C ₆ H ₄ 3, 5-H), 7.63 (s, 1H, C ₆ H ₃ 2-H ), 7.61 – 7.51 (m, 4H, anthracen-H), 7.45 (d, J = 8.3 Hz, 1H, C ₆ H ₃ , 5-H), 7.37 (d, J = 8.4 Hz, 1H, C ₆ H ₃ 6-H), 7.14 (s, 2H, CH=CH), consistent with the structural features.

Example 19 Synthesis of 2-(4-(2-(anthracene-9-yl)vinyl)phenyl)-5-(anthracene-9-yl)-1,3,4-oxadiazole (g)

(g)

Reaction steps (1), (2), (3) are the same as in Example 11, and the recrystallized product obtained in step (3) is the same as that in Example 11;

(4) 0.9g (1.91mmol) 4-(5-(anthracen-9-yl)-1,3,4-oxadiazol-2-yl) benzyl phosphonate and 0.39g (1.91mmol) 4-Methylaminobenzaldehyde is dissolved in 15ml N, and obtains solution in N-dimethylformamide, then in described solution, dripping is the dehydrated ethanol solution 6ml of 25% potassium tert-butoxide in the described solution, in Stir the reaction at 70°C for 5 h to obtain a reaction solution, cool and filter the reaction solution, and recrystallize the resulting filter cake with a mixture of dimethyl sulfoxide and ethanol at a volume ratio of 7:1 to obtain the final product. Yield: 82.1%. Proton NMR structure characterization data: ¹ H NMR (400 MHz, CDCl ₃ ) δ 8.71 (s, 1H, anthracen-H), 8.44 (s, 1H, anthracen-H), 8.38-8.33 (m, 2H, anthracen-H -H), 8.28 (d, J = 8.3 Hz, 2H, C ₆ H ₄ 2, 6-H), 8.16 – 8.07 (m, 4H, anthracen-H), 8.10 (d, J = 16.3 Hz, 1H, CH=CH) 8.06 – 7.99 (m, 2H, anthracen-H), 7.85 (d, J = _8.3 Hz, 2H, C6H43 _, 5-H), 7.82-7.63 (m, 4H, anthracen-H ), 7.53 – 7.43 (m, 4H, anthracen-H), 7.04 (d, J = 16.6 Hz, 1H, CH=CH), structural characterization data of C NMR spectrum: ¹³ C NMR (101 MHz, CDCl ₃ ) δ 165.70， 163.12， 140.82， 136.16， 131.95， 131.54， 131.51， 131.08， 129.72， 128.82， 127.80， 127.64， 127.60， 127.27， 127.02， 125.80， 125.76， 125.29， 125.13， 123.07， 117.27，符合结构特征。

Insect Growth and Development Inhibitory Activity Determination:

From the 19 final products prepared in Example 1 to Example 19, 12 compounds were selected as the test samples for the insect growth and development inhibitory activity test, and the insect growth and development inhibitory activity was measured by feeding weighing method: the feed was cut Form into uniform small pieces with a side length of 3 mm, and drop 200 μl of the test sample liquid on each piece of feed respectively (the test sample compound is configured as a dimethyl sulfoxide solution with a concentration of 0.8 mg/ml and 1.0 mg/ml ) to make a test sample, dry the test sample and place it in a petri dish, each of 10 beet armyworm and Trichoplusia larvae (provided by the State Key Laboratory of Biological Control, Sun Yat-Sen University) of the same age and size were inserted into each dish. Each experiment was repeated three times, and a blank control was set.

Body weight growth rate and weight growth inhibition rate are calculated according to the following formula: body weight growth rate=(average worm weight after treatment-average worm weight before treatment)/average worm weight after treatment, weight growth inhibition rate=(control weight growth rate-weight growth rate)/control weight growth rate. See Table 1 for the growth and development inhibitory activity of test sample compound (treatment concentration is 0.8mg/ml) to Trichoplusia larvae larvae on the 6th day, for test sample compound (treatment concentration is 1.0mg/ml) to beet armyworm larvae The growth and development inhibitory activity of the 8th day is shown in Table 2:

It can be seen from Table 1 and Table 2 that this class of compounds has significant growth and development inhibitory activities against Lepidopteran pests such as beet armyworm and Trichoplusia spp. Among them, the biological activities of compounds Ⅻ and g are particularly prominent. This type of compound has important application value for the development of environmentally friendly and efficient new insecticides.

Table 1

Table 2

Claims (5)

1. contain 3, the diphenyl ethylene derivatives of 4-oxadiazole is characterized in that described diphenyl ethylene derivatives concrete structure is as follows:

Ar wherein ₁, Ar ₂Be phenyl, 4-trifluoromethyl, 4-fluorophenyl, 4-chloro-phenyl-, 4-bromophenyl, 4-p-methoxy-phenyl, 4-nitrophenyl, 4-dimethylamino phenyl, 3-trifluoromethyl, 3-fluorophenyl, 3-chloro-phenyl-, 3-bromophenyl, 3-p-methoxy-phenyl, 3-nitrophenyl, 2-trifluoromethyl, 2-fluorophenyl, 2-chloro-phenyl-, 2-bromophenyl, 2-p-methoxy-phenyl, 2-nitrophenyl, 2,4-dichlorophenyl, 3,4-dichlorophenyl, 1-naphthyl or 9-anthryl.

2. according to claim 1ly contain 1,3, the diphenyl ethylene derivatives of 4-oxadiazole is characterized in that described Ar ₁And Ar ₂Identical.

3. according to claim 1ly contain 1,3, the diphenyl ethylene derivatives of 4-oxadiazole is characterized in that described Ar ₁And Ar ₂Different.

4. claim 1 is described contains 1,3, and the preparation method of the diphenyl ethylene derivatives of 4-oxadiazole is characterized in that comprising the steps:

(1) dioxide giving reaction

With equimolar aromatic aldehyde with the toluyl hydrazine is dissolved in ethanol, described ethanol and aromatic aldehyde and ethanol with the volume mol ratio of toluyl hydrazine is 3～4ml/mmol, must reaction solution behind heated and stirred backflow 0.5～2h; Cooling is also filtered described reaction solution, and dry cake obtains intermediate; Described intermediate is dissolved in ethanol, add chloramine-T again, get the intermediate reaction solution behind heated and stirred backflow 3～5h, after removing ethanol, last solid cooled and usefulness distilled water wash filter 23 ~ 5 times, dry cake, gained filter cake volume ratio are the distilled water and the acetone mixed solution recrystallization of 1:1 ~ 3, get recrystallized product A; The mol ratio of described intermediate and chloramine-T is 1:3～7, and the volume mol ratio of ethanol and intermediate is 10～20ml/mmol;

(2) N-bromo-succinimide bromo-reaction

With mol ratio is that the above-mentioned recrystallized product A and the N-bromo-succinimide of 1:1～1.5 is dissolved in tetracol phenixin, adding is the initiator Benzoyl Peroxide of 0.01 ~ 0.02:1 with the mass ratio of N-bromo-succinimide again, heating and stirring and refluxing get reaction solution, reaction end with thin-layer chromatography detection reaction liquid, after removing tetracol phenixin, last solid also filters with washing with alcohol; Be the tetrahydrofuran (THF) and the methyl alcohol mixed liquor recrystallization of 1:1 ~ 5 with volume ratio behind the filtration cakes torrefaction, recrystallized product B; The volume mol ratio 3～6ml/mmol of described tetracol phenixin and N-bromo-succinimide;

(3) triethyl-phosphite esterification

After mol ratio is the above-mentioned recrystallized product B and triethyl-phosphite mixed dissolution of 1:1.1～1.5, in temperature is stirring and refluxing 3～6h under 115～125 ℃ of conditions, after triethyl-phosphite excessive in the reaction system is removed in decompression, add normal hexane again and separate out solid product; Described solid product is the tetrahydrofuran (THF) and the normal hexane mixed solution recrystallization of 1:1～4 again with volume ratio, gets recrystallized product C;

(4) Wittig-Honner reaction

Equimolar aromatic aldehyde and the prepared recrystallized product C of step (3) are dissolved in N, get lysate in the dinethylformamide; In described lysate, add mass percent and be the ethanol solution of 15～30% potassium tert.-butoxide, get reaction solution, cool off and filter described reaction solution at 60～70 ℃ of following stirring reaction 5～9 h; Gained filter cake volume ratio is that dimethyl sulfoxide (DMSO) and the alcohol mixeding liquid recrystallization of 4～10:1 gets final product, promptly contains 1,3, the diphenyl ethylene derivatives of 4-oxadiazole; Described N, dinethylformamide is 10～15ml/ g with the volume mass ratio of recrystallized product C.

5. claim 1～3 is described contains 1,3, the application of the diphenyl ethylene derivatives of 4-oxadiazole in the active inhibition of insect growth growth.