CN108383755B - Method for synthesizing alkene dinitrile compound - Google Patents

Abstract

The invention discloses a method for synthesizing an enedinitrile compound, which comprises the steps of taking substituted aldehyde and malononitrile as raw materials, taking Ru/C as a catalyst, reacting in ethanol at 20-60 ℃, and after the reaction is completed, separating and purifying reaction liquid to obtain the enedinitrile compound; the Ru/C catalyst used in the invention is not only cheap and easy to obtain, but also can be recycled conveniently and repeatedly because the Ru/C catalyst is a heterogeneous catalyst system in the reaction; the reaction raw materials are various, cheap and easy to obtain, and are suitable for synthesizing various substituted alkene dinitrile compounds; simple post-treatment, good product purity and high yield.

Description

A kind of synthetic method of alkene nitrile compound

(1) Technical field

The invention relates to a method for synthesizing an enedionitrile compound.

(2) Background technology

Olefinitrile compounds are a kind of important bulk chemical intermediates, which are widely used in chemical industry, material, medicine, pesticide and other industries. For example, NK1 receptor antagonists have a good effect in the treatment of depression, and they can be used in tumor treatment; and nedionitriles can be used to synthesize NK1 receptor ligands (Recio R et al., European Journal of Medicinal Chemistry, 2017 , 138, 644-660.). Hassaneen, Hamdi M. et al. reported that a fused-ring compound with antibacterial activity could be synthesized from enedionitrile compounds (Journal of Heterocyclic Chemistry, 2017, 54(5), 2850-2858.).

The traditional method for synthesizing aralene nitriles is formed by the condensation and dehydration of aldehyde and malononitrile under alkaline conditions. alkaline wastewater, seriously polluting the environment.

(3) Contents of the invention

The object of the present invention is to provide a novel synthesis method for the enedionitrile compound represented by the formula (III), the method provides a new synthesis route, is simple in operation, convenient in post-processing, high in product yield and good in purity, In particular, the catalyst and solvent can be used repeatedly, which basically realizes zero discharge of raw and auxiliary materials, which not only saves production costs, but also reflects environmental friendliness, which is very suitable for large-scale industrial production.

The technical scheme adopted in the present invention is:

The present invention provides a method for synthesizing an enedionitrile compound represented by formula (III), which comprises the following steps: using a substituted aldehyde represented by formula (I) and a malononitrile represented by formula (II) as raw materials, and using Ru /C is used as a catalyst to react in ethanol at 20-60° C., after the reaction is complete, the reaction solution is separated and purified to obtain the enedionitrile compound represented by formula (III);

In formula (I), R is selected from one of the following groups: phenyl, substituted phenyl, furanyl, 2-thienyl or C1-C16 (preferably C3-C9) hydrocarbon group, and the substituted phenyl is ortho, Meta- or para-position substitution, the substituents of the substituted phenyl group are methyl, methoxy, nitro, halogen; R in formula (III) is the same as formula (I).

Further, the ratio of the amount of the substituted aldehyde shown in the formula (I) to the malononitrile feeding material is 1:1.

Further, the Ru/C dosage is based on the amount of Ru species, and the amount of the Ru species is 2‰˜10‰ of the amount of the substituted aldehyde species represented by formula (I).

Further, the volume dosage of ethanol is 5-10 ml/mmol based on the amount of the substituted aldehyde substance represented by formula (I).

Further, the method for separating and purifying the reaction solution is one of the following: (1) after the complete reaction, the reaction solution is filtered once to obtain a primary filtrate and a primary filter cake, and the primary filtrate recovers the organic solvent through a rotary evaporator; a primary filter cake After dissolving with dichloromethane, carry out secondary filtration to obtain secondary filtrate and secondary filter cake, and perform tertiary filtration after washing the secondary filter cake with dichloromethane to obtain tertiary filtrate and tertiary filter cake, and the third filter cake is Ru/ C catalyst is recycled, combined the secondary filtrate and the tertiary filtrate, and the dichloromethane is recovered by a rotary evaporator to obtain the enedionitrile compound shown in formula (III); (2) after the complete reaction, the reaction solution is filtered once to obtain The primary filter cake and the primary filtrate are washed with ethanol and then filtered for the second time to obtain the secondary filtrate and the secondary filter cake. The secondary filter cake is the Ru/C catalyst recycling. After the ethanol is recovered by a rotary evaporator, the enedionitrile compound represented by the formula (III) is obtained. Method (1) is used when the product is solid, and method (2) is used when the product is liquid.

)、戊烯基(

)、正丙基。式(I)所示取代醛为下列之一：苯甲醛、邻甲基苯甲醛、对甲基苯甲醛、对甲氧基苯甲醛、对硝基苯甲醛、间硝基苯甲醛、邻氯苯甲醛、对氯苯甲醛、对氟苯甲醛、2-噻吩甲醛、香茅醛、2-烯己醛、正丁醛。Further, in the described formula (I), R is selected from one of the following: phenyl, o-methylphenyl, p-methylphenyl, p-nitrophenyl, m-nitrophenyl, o-chlorophenyl, p-chlorophenyl Phenyl, p-fluorophenyl, 2-thienyl, 2,6-dimethyl-2-heptenyl (

), pentenyl (

), n-propyl. Substituted aldehyde shown in formula (I) is one of the following: benzaldehyde, o-tolualdehyde, p-tolualdehyde, p-methoxybenzaldehyde, p-nitrobenzaldehyde, m-nitrobenzaldehyde, o-chlorobenzene Formaldehyde, p-chlorobenzaldehyde, p-fluorobenzaldehyde, 2-thiophenecarboxaldehyde, citronellal, 2-enehexanal, n-butyraldehyde.

Further, the reaction temperature is 21-30° C., and the reaction time is 8-24 hours.

The carbon-supported ruthenium (Ru/C) catalyst used in the present invention can use commercially available products, and can also be prepared according to the method reported in the literature, and the Ru/C catalyst can be used.

Compared with the prior art, the beneficial effects of the present invention are:

1. The classical reaction of preparing enedionitrile compounds requires the addition of at least an equivalent amount of alkali to carry out the reaction, so the addition of a large amount of alkali seriously pollutes the environment and increases the pressure of post-reaction treatment for environmental protection. The present invention provides a novel method for synthesizing enedionitrile compounds catalyzed by ruthenium. The reaction can be performed under neutral conditions without the participation of a base, and the enedionitrile compounds can be prepared with a yield as high as 98%.

2. As shown in Figure 1, the process of the present invention skillfully realizes the "three major cycles" of the catalyst, the reaction solvent and the separation solvent, reduces the reaction cost, and most importantly, reduces the pollution to the environment and meets the requirements of green synthesis ; The specific cycle is as follows:

(1) The catalyst Ru/C used is not only cheap and easy to obtain, but also because it is a heterogeneous catalyst, it is easy to recover, and can be applied repeatedly, that is, catalyst recycling;

(2) the present invention realizes the recycling of reaction solvent (preferably ethanol);

(3) in the separation that the product is a solid phase, the present invention realizes the recycling of the separation solvent (preferably dichloromethane);

3, the separation and purification of the reaction of the present invention is simple (as shown in Figure 1, when the product is a liquid, after the reaction is finished, the catalyst is filtered off, and concentrated to obtain the product; as shown in Figure 2, when the product is a solid, the reaction is finished and filtered to recover. After ethanol, use dichloromethane to dissolve the filter cake, filter out the insoluble catalyst, and concentrate to obtain the product), and the product has good purity (up to 99%) and high yield (up to 99%), which not only saves production costs , and reflects the environmental friendliness, which is very suitable for industrialized large-scale production.

4. Looking at the whole process flow, the raw materials (malononitrile and aldehyde) of the process of the present invention enter the reaction system, and after the reaction of the system, the product enedionitrile compounds leave the reaction system, and the reaction cycle of the system is realized, and there is no by-product in the middle. Produced, the utilization rate of raw materials is high. Therefore, the present invention is an efficient and green synthesis method of substituted enedionitrile compounds.

5. The substrate of the reaction of the present invention has a wide spectrum, which can be various substituted aromatic aldehydes or aliphatic aldehydes.

6. The reaction of the present invention is a room temperature reaction, and neither heating nor cooling is required for the reaction, thereby saving energy.

(4) Description of drawings

Fig. 1 The present invention embodies the process route cycle diagram of efficient green synthesis (the product is liquid).

Fig. 2 The present invention embodies the process route cycle diagram of efficient green synthesis (the product is solid).

(5) Specific implementation manner

The present invention is further described below in conjunction with specific embodiment, but the protection scope of the present invention is not limited to this:

The Ru/C used in the examples of the present invention was purchased from Conner New Materials (Hangzhou) Co., Ltd., the model is K0803, and the Ru content is 5% (g/g).

The room temperature in the present invention refers to 21-30°C.

Example 1: Preparation of enedionitrile compound (III-1)

The reaction formula is as follows:

Add 5.306g (50mmol) of benzaldehyde (I-1), 0.5g (Ru molar weight is 5‰ of (I-1)) Ru/C catalyst, 3.303g (50mmol) of malononitrile ( II) and 100 mL of ethanol, stirred and reacted at room temperature for 12 h, and GC-MS detected that the reaction of the raw materials was complete, and the reaction was stopped. The reaction solution was filtered once to obtain a primary filtrate and a primary filter cake, and the primary filtrate was subjected to a rotary evaporator to recover ethanol; the primary filter cake was dissolved in 50 mL of dichloromethane, and filtered for a second time to obtain a secondary filtrate and a secondary filter cake. The secondary filter cake was washed with dichloromethane and filtered three times to obtain the tertiary filtrate and the tertiary filter cake. The tertiary filter cake was the Ru/C catalyst and could be used for the next batch of reactions. The secondary filtrate and the tertiary filtrate were combined, and the second filtrate was recovered by a rotary evaporator. Methyl chloride was used for the next batch of reaction, and 7.631 g of solid was obtained at the same time, the yield was 99.0%, and the GC-MS purity was 99.0%. The structure of compound formula (III-1) is characterized as follows:

¹ H-NMR (CDCl ₃ , 500MHz): δ 7.93-7.91(m, 2H), 7.80(s, 1H), 7.66-7.63(m, 1H), 7.57-7.54(m, 2H); ¹³ C- NMR (CDCl ₃ , 125MHz): δ 160.0, 134.8, 131.1, 130.8, 129.8, 113.8, 112.7, 83.0; GC-MS (EI): m/z 154 [M ⁺ ].

Example 2: Preparation of enedionitrile compound (III-2)

The reaction formula is as follows:

Add 6.008g (50mmol) of o-methylbenzaldehyde (I-2), 0.5g (Ru molar weight is 5‰ of (1-2)) Ru/C catalyst, 3.303g (50mmol) of propylene into the reaction flask. The dinitrile (II) and 100 mL of ethanol were reacted with stirring at room temperature for 14 h. The following operations were the same as those in Example 1. Finally, 8.242 g of solid was obtained, the yield was 98.0%, and the GC-MS purity was 99.0%. The structure of compound formula (III-2) is characterized as follows:

¹ H-NMR (CDCl ₃ , 500MHz): δ 8.12(s, 1H), 8.11-8.09(m, 1H), 7.38-7.33(m, 2H), 2.46(s, 3H); ¹³ C-NMR( CDCl ₃ , 125MHz): δ158.2, 139.8, 134.3, 131.5, 130.0, 128.4, 127.1, 113.9, 112.5, 84.1, 19.9; GC-MS(EI): m/z 168[M ⁺ ].

Example 3: Preparation of enedionitrile compound (III-3)

The reaction formula is as follows:

To the reaction flask, add 6.008g (50mmol) of p-methylbenzaldehyde (I-3), 0.5g (Ru molar weight is 5‰ of (I-3)) Ru/C catalyst, 3.303g (50mmol) of propylene Dinitrile II and 80 mL of ethanol were stirred at room temperature for 10 h, and the following operations were the same as in Example 1. Finally, 8.326 g of solid was obtained, the yield was 99.0%, and the GC-MS purity was 99.0%. The structure of compound formula (III-3) is characterized as follows:

¹ H-NMR (CDCl ₃ , 500MHz): δ 8.20 (d, J=8.1 Hz, 2H), 7.73 (s, 1H), 7.35 (d, J=8.1 Hz, 2H), 2.47 (s, 3H) ; ¹³ C-NMR (CDCl ₃ , 125MHz): δ 159.8, 146.4, 130.9, 130.4, 128.4, 114.0, 112.9, 81.1, 22.0; GC-MS (EI): m/z 168 [M ⁺ ].

Example 4: Preparation of enedionitrile compound (III-4)

The reaction formula is as follows:

Add 6.808g (50mmol) of p-methoxybenzaldehyde (I-4), 0.5g (Ru molar weight is 5‰ of (1-4)) Ru/C catalyst, 3.303g (50mmol) of Ru/C catalyst into the reaction flask. Malononitrile (II) and 120 mL of ethanol were stirred at room temperature for 12 h, and the following operations were the same as in Example 1. Finally, 9.118 g of solid was obtained, the yield was 99.0%, and the GC-MS purity was 99.0%. The structure of compound formula (III-4) is characterized as follows:

¹ H NMR (CDCl ₃ , 500 MHz): δ 7.91 (d, J=8.9 Hz, 2H), 7.67 (s, 1H), 7.02 (d, J=8.9 Hz, 2H), 3.93 (s, 3H); ¹³ C NMR (CDCl ₃ , 125MHz): δ 164.9, 155.9, 133.5, 124.1, 115.2, 114.5, 113.4, 78.6, 55.9; GC-MS (EI): m/z 184 [M ⁺ ].

Example 5: Preparation of enedionitrile compound (III-5)

The reaction formula is as follows:

Add 7.556g (50mmol) of p-nitrobenzaldehyde (I-5), 0.75g (Ru molar weight is 7.5‰ of (I-5)) Ru/C catalyst, 3.303g (50mmol) of propylene into the reaction flask. Dinitrile II and 130 mL of ethanol were stirred at room temperature for 18 h, and the following operations were the same as in Example 1. Finally, 9.700 g of solid was obtained, the yield was 97.4%, and the GC-MS purity was 99.0%. The structure of compound formula (III-5) is characterized as follows:

¹ H NMR (CDCl ₃ , 500MHz) δ 8.39 (d, J=8.8 Hz, 2H), 8.08 (d, J=8.8 Hz, 2H), 7.89 (s, 1H); ¹³ C NMR (CDCl ₃ , 125 MHz) δ156.9, 150.3, 135.1, 131.4, 124.6, 112.6, 111.7, 87.5; GC-MS(EI): m/z 199[M ⁺ ].

Example 6: Preparation of olefinonitrile compound (III-6)

The reaction formula is as follows:

To the reaction flask, add 7.556g (50mmol) of m-nitrobenzaldehyde (I-6), 1.0g (Ru molar weight is 7.5‰ of (I-6)) Ru/C catalyst, 3.303g (50mmol) of propylene Dinitrile II and 130 mL of ethanol were stirred at room temperature for 24 h, and the following operations were the same as in Example 1. Finally, 9.520 g of solid was obtained, the yield was 95.6%, and the GC-MS purity was 98.0%. The structure of compound formula (III-6) is characterized as follows:

¹ H NMR (CDCl ₃ , 500MHz) δ 8.68 (s, 1H), 8.48 (d, J=8.0 Hz, 1H), 8.34 (d, 1H), 7.91-7.75 (m, 2H); ¹³ C NMR ( CDCl ₃ , 125MHz)δ157.2,148.7,134.9,132.0,131.1,128.3,115.9,112.7,111.7,86.9; GC-MS(EI):m/z 199[M ⁺ ].

Example 7: Preparation of enedionitrile compound (III-7)

The reaction formula is as follows:

Add 7.029g (50mmol) of o-chlorobenzaldehyde (I-7), 0.5g (Ru molar weight is 5‰ of (1-7)) Ru/C catalyst, 3.303g (50mmol) of propanediol into the reaction flask Nitrile (II) and 100 mL of ethanol were stirred at room temperature for 15 h, and the following operations were the same as in Example 1. Finally, 9.053 g of solid was obtained, the yield was 96.0%, and the GC-MS purity was 98.0%. The structure of compound formula (III-7) is characterized as follows:

¹ H NMR (CDCl ₃ , 500MHz) δ 8.28 (s, 1H), 8.18 (d, J=7.9Hz, 1H), 7.56 (d, J=4.2Hz, 2H), 7.48-7.44 (m, 1H) . ¹³ C NMR (CDCI _3, 125MHz) δ 156.1, 136.4, 135.1, 130.8, 129.6, 129.1, 127.9, 113.3, 112.0, 85.9; GC-MS(EI): m/z 188[M] ⁺ ,190[M+ 2] ⁺ .

Example 8: Preparation of olefinonitrile compound (III-8)

The reaction formula is as follows:

Into the reaction flask, add 7.029g (50mmol) of p-chlorobenzaldehyde (I-8), 0.5g (Ru molar weight is 5‰ of (1-8)) Ru/C catalyst, 3.303g (50mmol) of propanediol Nitrile (II) and 100 mL of ethanol were stirred at room temperature for 15 h, and the following operations were the same as in Example 1. Finally, 9.242 g of solid was obtained, the yield was 98.0%, and the GC-MS purity was 99.0%. The structure of compound formula (III-8) is characterized as follows:

¹ H NMR (CDCI ₃ , 500MHz) δ 7.86 (d, J=8.52 Hz, 2H), 7.74 (s, 1H), 7.53 (d, J=8.52 Hz, 2H); ¹³ C NMR (CDCI _3, 125 MHz) )δ158.3,141.2,131.9 130.2,129.3,113.5,112.4,83.5; GC-MS(EI): m/z 188[M] ⁺ ,190[M+2] ⁺ .

Example 9: Preparation of olefinonitrile compound (III-9)

The reaction formula is as follows:

To the reaction flask, add 6.454g (50mmol) of p-fluorobenzaldehyde (I-9), 0.5g (Ru molar weight is 5‰ of (I-9)) Ru/C catalyst, 3.303g (50mmol) of propanediol Nitrile (II) and 100 mL of ethanol were stirred at room temperature for 12 h, and the following operations were the same as in Example 1. Finally, 8.418 g of solid was obtained, the yield was 97.8%, and the GC-MS purity was 98.0%. The structure of compound formula (III-9) is characterized as follows:

¹ H NMR (CDCI ₃ , 600MHz) δ 7.80-7.97 (m, 2H), 7.77 (s, 1H), 7.28-7.24 (m, 2H); ¹³ CNMR (CDCI _3, 150 MHz) δ 166.2 (d, J=258.7Hz), 158.4, 133.5(d, J=9.5Hz), 127.4(d, J=3.3Hz), 117.3(d, J=22.0Hz), 113.6, 112.6, 82.4(d, J=2.7Hz) ); GC-MS(EI): m/z 172[M] ⁺ .

Example 10: Preparation of enedionitrile compound (III-10)

The reaction formula is as follows:

Add 5.068g (50mmol) of 2-thiophenecarboxaldehyde (I-10), 0.5g (Ru molar weight is 5‰ of (I-10)) Ru/C catalyst, 3.303g (50mmol) of propanediol into the reaction flask Nitrile II and 100 mL of ethanol were stirred and reacted at room temperature for 15 h, and the following operations were the same as in Example 1. Finally, 7.769 g of solid was obtained, the yield was 97.0%, and the GC-MS purity was 98.0%. The structure of compound formula (III-10) is characterized as follows:

¹ H NMR (CDCI ₃ , 500MHz) δ 7.92-7.91 (m, 1H), 7.84-7.82 (m, 2H), 7.31-7.29 (m, 1H); ¹³ C NMR (CDCI _3, 125 MHz) δ 151.4, 138.3 , 137.2, 135.5, 129.2, 113.9, 113.2, 78.4; GC-MS(EI): m/z 160[M] ⁺ .

Example 11: Preparation of olefinic nitriles (III-11)

The reaction formula is as follows:

Add 7.713g (50mmol) of citronellal (I-11), 1.0g (Ru molar weight is 10‰ of (I-11)) Ru/C catalyst, 3.303g (50mmol) of malononitrile into the reaction flask II and 100 mL of ethanol were stirred and reacted at room temperature for 24 h. GC-MS detected that the reaction of the raw materials was complete, and the reaction was stopped. The reaction solution is filtered once to obtain a primary filter cake and a primary filtrate, wash the primary filter cake with 5 mL of ethanol, and filter it for a second time to obtain a secondary filtrate and a secondary filter cake. The secondary filter cake is a Ru/C catalyst, which can be used for In the next batch of reactions, the primary filtrate and the secondary filtrate were combined to recover ethanol by a rotary evaporator for the next batch of reactions; at the same time, 9.104 g of a liquid product was obtained with a yield of 90.0% and a GC-MS purity of 97.0%. The structure of compound formula (III-11) is characterized as follows:

¹ H NMR (CDCl ₃ , 500MHz) δ7.37(t, J=8.0Hz, 1H), 5.07-5.05(m, 1H), 2.62-2.55(m, 1H), 2.49-2.43(m, 1H), 2.07-1.99(m, 2H), 1.82-1.78(m, 1H), 1.69(s, 3H), 1.61(s, 3H), 1.40-1.25(m, 2H), 0.98(d, J=6.7Hz, 3H); GC-MS (EI): m/z 202[M] ⁺ .

Example 12: Preparation of enedionitrile compound (III-12)

The reaction formula is as follows:

Add 4.908g (50mmol) of 2-enehexanal (I-12), 1.0g (Ru molar weight is 10‰ of (I-12)) Ru/C catalyst, 3.303g (50mmol) of propylene into the reaction flask. Dinitrile II and 100 mL of ethanol were stirred at room temperature for 24 h, and the following operations were the same as in Example 11. Finally, 6.608 g of solid was obtained, the yield was 90.2%, and the GC-MS purity was 97.2%. The structure of compound formula (III-12) is characterized as follows:

¹ H NMR (CDCl ₃ , 600MHz) δ7.47(d, J=10.3Hz, 1H), 6.69-6.65(m, 2H), 2.36-2.32(m, 2H), 1.57-1.53(m, 2H), 0.98 (t, J=7.4 Hz, 3H); ¹³ C NMR (CDCl ₃ , 150 MHz) δ 160.9, 157.4, 126.1, 113.3, 111.4, 82.5, 35.8, 21.4, 13.7; GC-MS (EI): m/z 146 [M ⁺ ].

Example 13: Preparation of enedionitrile compound (III-13)

The reaction formula is as follows:

Into the reaction flask, add 3.606g (50mmol) of n-butyraldehyde (I-13), 1.0g (Ru molar weight is 10‰ of (I-13)) Ru/C catalyst, 3.303g (50mmol) of malononitrile II and 100 mL of ethanol were stirred and reacted at room temperature for 24 h, and the following operations were the same as those in Example 11. Finally, 5.611 g of solid was obtained, the yield was 93.4%, and the GC-MS purity was 98.0%. The structure of compound formula (III-13) is characterized as follows:

¹ H NMR (CDCl ₃ , 600MHz) δ 7.38 (t, J=8.0Hz, 1H), 2.64-2.54 (m, 2H), 1.70-1.57 (m, 2H), 1.02 (t, J=7.4Hz, 3H); ¹³ C NMR (CDCl ₃ , 150MHz) δ 170.0, 112.3, 110.7, 89.9, 34.8, 21.1, 13.6; GC-MS (EI): m/z 120 [M ⁺ ].

Example 14: Recovery of catalyst and solvent

The reaction formula is as follows:

Add 5.306g (50mmol) of benzaldehyde (I-1), 0.5g (Ru molar weight is 5‰ of (I-1)) Ru/C catalyst, 3.303g (50mmol) of malononitrile II into the reaction flask and 100 mL of ethanol, the reaction was stirred at room temperature for 14 h, and GC-MS detected that the reaction of the raw materials was complete, and the reaction was stopped. The reaction solution was filtered once to obtain a primary filtrate and a primary filter cake, and the primary filtrate was subjected to a rotary evaporator to recover ethanol; the primary filter cake was dissolved in 50 mL of dichloromethane, and filtered for a second time to obtain a secondary filtrate and a secondary filter cake. The secondary filter cake was washed with dichloromethane and filtered three times to obtain the tertiary filtrate and the tertiary filter cake. The tertiary filter cake was the Ru/C catalyst and could be used for the next batch of reactions. The secondary filtrate and the tertiary filtrate were combined, and the second filtrate was recovered by a rotary evaporator. Chloromethane is used for the next batch of reactions, and the compound formula (III-1) is obtained at the same time, and the structural characterization of the compound formula (III-1) is the same as that in Example 1.

The catalyst and solvent recovered in the above experiments were put into the next batch of reactions. The experiment was repeated five times, and the results are shown in Table 1:

Table 1

Example 15: Catalyst Screening Experiment

The reaction formula is as follows:

To the reaction flask, add 5.306g (50mmol) of benzaldehyde (I-1), catalyst (the metal palladium mass loading in palladium carbon is 5%), 3.303g (50mmol) of malononitrile (II) and 100mL of ethanol , the reaction was stirred at room temperature for 12h, and GC-MS detected that the reaction of the raw materials was complete.

Table 2

Note: The catalysts in the table were purchased from Annagy Chemical Sahn Chemical Technology (Shanghai) Co., Ltd.

Claims (6)

1. a synthetic method of an enedionitrile compound shown in formula (III), characterized in that the method is: with the substituted aldehyde shown in formula (I) and malononitrile shown in formula (II) as raw materials, Using Ru/C as a catalyst, the reaction is carried out in ethanol at 20-60 ° C, and after the reaction is completed, the reaction solution is separated and purified to obtain the enedionitrile compound represented by formula (III);

In formula (I), R is selected from one of the following groups: phenyl, o-methylphenyl, p-methylphenyl, p-nitrophenyl, m-nitrophenyl, o-chlorophenyl, p-chlorobenzene base, p-fluorophenyl, 2-thienyl, 2,6-dimethyl-2-heptenyl, pentenyl, n-propyl; R in formula (III) is the same as formula (I). 2. the synthetic method of enedionitrile compound as claimed in claim 1 is characterized in that the ratio of the amount of substituted aldehyde shown in the formula (I) and malononitrile feeding material is 1:1. 3. the synthetic method of enedionitrile compound as claimed in claim 1 is characterized in that described Ru/C consumption is in the amount of Ru substance, and the amount of described Ru substance is the substituted aldehyde substance shown in formula (I). 2‰ to 10‰ of the amount. 4. The method for synthesizing enedionitrile compounds according to claim 1, wherein the volumetric consumption of the ethanol is calculated as 5-10 ml/mmol in terms of the amount of the substituted aldehyde substance represented by the formula (I). 5. the synthetic method of enedionitrile compound as claimed in claim 1 is characterized in that the method for separation and purification of described reaction solution is one of the following: (1) after complete reaction, the reaction solution is filtered once to obtain a filtrate and the primary filter cake, and the primary filtrate is recycled through a rotary evaporator; the primary filter cake is dissolved in dichloromethane and then filtered for a second time to obtain a secondary filtrate and a secondary filter cake, and the secondary filter cake is washed with dichloromethane. Filter three times to obtain three filtrates and three filter cakes, and the three filter cakes are Ru/C catalyst recycling; Merge the second filtrate and the third filtrate, and obtain enedionitrile shown in formula (III) after the dichloromethane is recovered by a rotary evaporator (2) after the complete reaction, filter the reaction solution once to obtain a filter cake and a filtrate, wash the filter cake with ethanol and perform a second filter to obtain a second filtrate and a filter cake, and filter the second time The cake is the Ru/C catalyst recycling, and the primary filtrate and the secondary filtrate are combined to recover ethanol through a rotary evaporator to obtain the enedionitrile compound represented by formula (III). 6 . The method for synthesizing enedionitrile compounds according to claim 1 , wherein the reaction temperature is 21-30° C. and the reaction time is 8-24 hours. 7 .

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