CN106083843B - Macrocyclic amide metal complex and its preparation method and application - Google Patents

Abstract

The present invention provides a kind of macrocyclic amide metal complexs and its preparation method and application.The structural formula of the metal complex is shown in formula I；Formulas I:Wherein, R CH₃Or one of F, M Fe, Co, Mn or Cu, M ' are K, Na or Li.The application also provides a kind of method for preparing the metal complex, and the method includes first stage reaction, second stage reaction and phase III reactions.The application also provides a kind of application of metal complex, the oxidation reaction applied to alcohol type organic and aldehydes organic matter.Metal complex provided by the present application, it can be prepared by a variety of routes, preparation process is short, it is easy to operate, raw material sources used are abundant, and property is stablized, and central metal is not belonging to noble metal, cheap and non-toxic or toxicity is low, such complex has good application performance in the oxidation reaction.

Description

Macrocyclic amide metal complex and its preparation method and application

technical field

The invention relates to the field of catalysts, in particular, to a macrocyclic amide metal complex and a preparation method and application thereof.

Background technique

Oxidation is one of the most important reactions in chemistry and chemical industry, and occupies a very important position in both laboratory and industry. High-valence transition metal oxides or their salts such as permanganate, dichromate, etc. were once the first choice for oxidation reactions due to their rapid reaction and simple operation. , a new type of oxidation system with better selectivity, among which macrocyclic metal complexes have become an important research direction because of their good reactivity and selectivity.

The so-called macrocyclic complex refers to a cyclic complex formed by the coordination of a polydentate ligand with a plurality of coordination atoms such as O, N, S, P, etc. on the skeleton of the ring and a metal. Macrocyclic metal complexes are ubiquitous in organisms and participate in many chemical processes of life processes, which are of great significance for revealing the chemical nature of life phenomena. In addition, some macrocyclic complexes also have special molecular recognition, catalytic oxidation, electrical, optical, thermal and other functions, which are of great significance to the development of new materials and new technologies. Therefore, it has attracted more and more attention from chemists and biologists.

At present, scientists from various countries have carried out extensive explorations on the synthesis and preparation of new macrocyclic metal complexes for catalytic oxidation and other chemical processes. However, there are problems such as low structural stability, low utilization rate of repeated catalysis, long process route, and high synthesis cost, which limit the application of such metal complexes. Therefore, designing and synthesizing new highly active complexes, developing concise and efficient preparation processes, and reducing the cost of use are the focus of future research.

In view of this, the present invention is proposed.

SUMMARY OF THE INVENTION

The first object of the present invention is to provide a metal complex, the metal complex has the advantages of high catalytic activity, low use concentration, fast speed, stable structure, etc., and the metal complex can catalyze the participation of hydrogen peroxide in green oxidation process.

The second object of the present invention is to provide a method for preparing the metal complex, which has the advantages of mild reaction conditions, readily available raw materials, low cost, and high yield.

In order to realize the above-mentioned purpose of the present invention, the following technical solutions are specially adopted:

A macrocyclic amide metal complex, the structural formula of the metal complex is shown in formula I;

Formula I:

Wherein, R is CH ₃ or F, M is one of Fe, Co, Mn or Cu, M' is K, Na or Li; n=1 or 2.

A method for preparing the macrocyclic amide metal complex, the method comprising a first-stage reaction, a second-stage reaction and a third-stage reaction,

The first stage reaction includes:

A1. under inert gas atmosphere, in the system that 2-aminoisobutyric acid and anhydrous pyridine are formed, drip dimethylmalonyl chloride, after the reaction is finished, remove the solvent to obtain oil, and the oil is adjusted to pH to 2-3, suction filtration to obtain dimethylmalonamide diacid;

or,

A2. In an inert gas atmosphere, using anhydrous pyridine as a solvent, 2-aminoisobutyric acid and diethyl dimethyl malonate or diethyl difluoromalonate are heated and closed for reaction, and the solvent is removed after the reaction is completed To obtain an oily substance, adjust the pH of the oily substance to 2-3, and perform suction filtration to obtain dimethylmalonamide diacid or difluoromalonamide diacid;

The second stage reaction includes:

B. Under an inert gas atmosphere, add dimethylmalonamide diacid or difluoromalonamide diacid, anhydrous 1,2-dichloroethane to the reaction vessel successively, and then dropwise add dichloroethane The sulfoxide is heated to reflux after the dropwise addition, reacts for 6-10 h, and removes the solvent to obtain dimethylmalonamide dichloride or difluoromalonamide dichloride;

The third stage reaction includes:

C. Under an inert gas atmosphere, successively add the dimethylmalonamide dichloride or difluoromalonamide diacid chloride, anhydrous treated dichloromethane obtained in the above step B into the reaction vessel, and then dropwise add triethyl amine, add 3,4-diaminopyridine in batches at the same time, remove the solvent after the reaction, then add water to vigorously stir, suction filtration, and use chromatographic column gradient elution to separate the filtrate to obtain the compound shown in formula II after rotary evaporation;

Formula II:

R is _CH3 or F;

D. Under an inert gas atmosphere, add the compound shown in formula II and the first solvent to the reaction vessel, then slowly add a strong base, after the reaction for 0.5-1.5h, add anhydrous metal salt, and stir the reaction at room temperature for 12-24h, The product shown in formula I is obtained through post-processing steps;

Or a third-stage reaction consists of:

E. under the protection of inert gas, the dimethylmalonamide dichloride or difluoromalonamide dichloride obtained in the above step B, the anhydrous metal salt are added in the reaction vessel, the second solvent is added, and then slowly dripped Triethylamine, 3,4-diaminopyridine was added in batches under stirring at the same time, and after 6-10 h of reaction, the product shown in formula I was obtained through the post-processing steps.

The preparation of its first stage can generate amide bond through the acylation of conventional acid chloride and amine (conventional method), and also can use ester raw material with more readily available, easy to store and stable properties to replace the direct aminolysis of corresponding acid chloride and amine. To generate amide bonds, in the metal coordination of the third-stage reaction, the conventional method of ring formation, alkali treatment and metal coordination can be used, or the direct ring-closure coordination one-step method induced by the metal ion template method can be used to make such substances There are many more routes for the preparation of , and the strengths of different methods can be combined. The method has a short preparation route and does not require any protection and deprotection operations of functional groups. Especially in the preparation of the intermediate diamide diacid, malonate raw materials can be directly used for aminolysis, which makes the selection of raw materials more diverse. The raw materials have good stability and storage resistance. The solvents used are all common solvents, which are cheap and easy to obtain. In some reactions, the solvent also acts as an acid scavenger.

Preferably, in the step A1, the reaction temperature is controlled to be 60-70°C, and the reaction time is 10-15h; in the step A2, the reaction temperature is controlled to be 180-240°C, and the reaction time is 1-3h.

In steps A1 and A2, the method A2 of direct aminolysis of malonate with aminoisobutyric acid is preferably employed.

More preferably, the first solvent is anhydrous dichloromethane or anhydrous THF, the second solvent is anhydrous pyridine or anhydrous dimethylformamide; the strong base is KHMDS , LiHMDS, potassium tert-butoxide or sodium tert-butoxide.

It is particularly emphasized that the choice of basic substances has a significant impact on the mildness of the reaction conditions and the convenience of operation. The basic substance selected and used in step E is triethylamine, which has mild reaction conditions, convenient operation and low price, and has more advantages than organic strong bases such as KHDMS.

Preferably, the anhydrous metal salt is anhydrous ferric chloride, anhydrous cobalt chloride, anhydrous copper chloride, anhydrous copper acetate or anhydrous manganese dichloride.

Preferably, in the step C, the eluents used in the chromatographic column elution and separation are methanol and dichloromethane, and the volume ratio of methanol to dichloromethane in the eluent is 1:30-1:5.

Preferably, in the step D, the post-processing step is specifically:

The reaction system was suction filtered, the filter cake was washed with ethanol, then the filter cake was dissolved in isopropanol, and the filtrate was rotary evaporated to obtain a solid after filtration;

The solid matter is dissolved in water, and after filtration, the filtrate is rotary evaporated to obtain the product shown in formula I.

Optionally, in the step A1 or A2, after adjusting the pH, it is allowed to stand for 1-2 hours before suction filtration, and the filter cake is washed 2-3 times with acetonitrile.

The present application also provides an application of the macrocyclic amide metal complex, which is applied to the oxidation reaction of alcohol organic compounds or aldehyde organic compounds.

The present application also provides an application of the macrocyclic amide metal complex, which is applied to the oxidative degradation of wastewater containing refractory organic pollutants.

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

(1) The metal complex provided by the application has good catalytic effect, fast reaction speed, stable structure, high repeatable catalytic efficiency and wide applicable pH range;

(2) The preparation method provided by the application has mild reaction conditions, high yield and low cost, and is suitable for large-scale industrial production;

(3) The metal complexes provided by the present application can be widely used in the catalytic oxidation reaction of organic compounds, especially in the oxidation reaction of alcohol organic compounds and aldehyde organic compounds and the degradation of dye wastewater, and can quickly remove COD.

Description of drawings

In order to illustrate the embodiments of the present invention or the technical solutions in the prior art more clearly, the following briefly introduces the accompanying drawings that are required to be used in the description of the embodiments or the prior art.

Figure 1 is the HNMR of the compound of formula II provided in Example 1 of the application;

Figure 2 is the ESI-MS of the compound of formula II provided in Example 1 of the application;

Figure 3 is the IR of the compound of formula II provided in Example 1 of the application;

Figure 4 is the HNMR of the compound of formula II provided in Example 2 of the application;

Figure 5 is the CNMR of the compound of formula II provided in Example 2 of the application;

Figure 6 is the ESI-MS of the compound of formula II provided in Example 2 of the application;

Figure 7 is the ESI-MS of the compound of formula I provided in Example 3 of the application;

Figure 8 is the IR of the compound of formula I provided in Example 3 of the application;

Figure 9 is the ESI-MS of the compound of formula I provided in Example 4 of the application;

Figure 10 is the IR of the compound of formula I provided in Example 4 of the application;

Figure 11 is the ESI-MS of the compound of formula I provided in Example 5 of the application;

Figure 12 is the IR of the compound of formula I provided in Example 5 of the application;

Figure 13 is the ESI-MS of the compound of formula I provided in Example 6 of the application;

Figure 14 is the IR of the compound of formula I provided in Example 6 of the application;

Figure 15 is the ESI-MS of the compound of formula I provided in Example 7 of the application;

Figure 16 is the IR of the compound of formula I provided in Example 7 of the application;

Figure 17 is the ESI-MS of the compound of formula I provided in Example 8 of the application;

Figure 18 is the structure of the dye Basic Red 46 used in Example 10 of the application;

Figure 19 is the structure of the dye Basic Yellow 13 used in Example 10 of the application;

Figure 20 is the structure of the dye basic blue 41 used in Example 10 of the application;

Figure 21 is the structure of the dye cation black X-RL used in Example 10 of the application;

Among them, R=CH ₃ in the compound of formula I or II of the accompanying drawings 1-16, R=F in the compound of formula I of the accompanying drawings 17; M=Fe in the drawings 7-8 and 15-17, M=Co in Figures 9-10, M=Cu in Figures 11-12, and M=Mn in Figures 13-14.

Detailed ways

The embodiments of the present invention will be described in detail below with reference to the examples, but those skilled in the art will understand that the following examples are only used to illustrate the present invention and should not be regarded as limiting the scope of the present invention. If the specific conditions are not indicated in the examples, it is carried out according to the conventional conditions or the conditions suggested by the manufacturer. The reagents or instruments used without the manufacturer's indication are conventional products that can be purchased from the market.

Example 1

In a 250mL three-necked flask equipped with a constant pressure dropping funnel and argon protection, a magnet was added and connected to argon protection, followed by adding 2-aminoisobutyric acid (10g, 97mmol), anhydrous pyridine (150mL), stirring at room temperature Then, freshly prepared dimethylmalonyl chloride (8.2 mL, 63 mmol) was slowly added into the constant pressure dropping funnel. After 1 h, the dropwise addition was completed. 3M hydrochloric acid (30 mL) was adjusted to pH 2～3, and a large amount of solid was precipitated. After standing at low temperature for 1 h, suction filtration was performed, and the filter cake was washed three times with a small amount of acetonitrile to obtain 11.6 g of white solid powder, which was dried and weighed, with a yield of 75%.

In a 100mL three-necked flask equipped with a constant pressure dropping funnel and an argon gas protection, the magnetron was added successively, the above obtained dimethylmalonamide diacid (4g, 12mmol), 1,2-dichloroethane (30mL) , start stirring, slowly add thionyl chloride (10 mL, 120 mmol) to the three-necked flask through a constant pressure dropping funnel at room temperature, and then heat up to reflux after the dropwise addition, and stop the reaction after 8 h. After removing the solvent on a rotary evaporator, 3.7 g of a pale yellow solid powder (diamide diacid chloride 1) was obtained in a yield of 90%.

Add 2g (5.9mmol) of the above-mentioned solid (dimethylmalonamide diacid chloride) into a 100ml three-necked flask at room temperature and under argon protection, add dry dichloromethane (30mL), and slowly add dropwise from a constant pressure dropping funnel Triethylamine (5 mL, 32 mmol) was added in batches with 3,4-diaminopyridine (0.64 g, 5.9 mmol) under stirring, and the reaction was monitored by TLC until the raw materials disappeared, and the reaction was continued for 1 h. The solvent was removed on a rotary evaporator, water was added, vigorously stirred, suction filtered, the filtrate was rotary evaporated to dryness, and separated by column chromatography (gradient elution with methanol and dichloromethane) to obtain 1.9 g of the compound of formula II as a white powder with a yield of 85.0%.

Table 1 NMR H spectrum analysis of the product of formula II

The attribution results of the nuclear magnetic resonance spectrum in the above table are given according to the structure number shown in Figure 1. From Figure 1, the hydrogen on the primary amino group has disappeared, and 4 appear at δ=7.81, 7.88, 8.39 and 8.72ppm, respectively. A peak of amide H, δ=1.47～1.50ppm, a peak with H number of 18 appears, which is the hydrogen of another 6 methyl groups on the ring, indicating that dimethylmalonyl chloride reacts with the deprotected half-ring in a 1:1 reaction to form a ring product.

Its high-resolution mass spectrum is shown in Figure 2.

The relative molecular weight of the expected product is 375, and the (M+H) ion peak of the target product at m/z=376 can be seen from the mass spectrum.

Its infrared spectrum is shown in Figure 3.

Its carbonyl peak at the wavenumber of 1670 cm ^-1 can be seen.

Example 2

In a stainless steel pressure-resistant reactor (50mL), add magnetron, 2-aminoisobutyric acid (4g, 38.8mmol), anhydrous pyridine (30mL), diethyl dimethylmalonate (6.4mL, 38.8mmol) in turn mmol), the reaction kettle was closed after the argon gas was replaced for 3 times, the temperature was raised to 200 ° C in an oil bath and maintained for 2 h, the reaction solution was removed after cooling, and the pyridine was removed on a rotary evaporator to obtain an oily substance, which was added 3M hydrochloric acid (15 mL) to adjust. When the pH reached 2-3, a large amount of solid was precipitated. After standing at low temperature for 1 hour, suction filtration was performed, and the filter cake was washed three times with a small amount of acetonitrile to obtain a white solid powder, which was dried and weighed 5.2 g, with a yield of 83%.

In a 100mL three-necked flask equipped with a constant pressure dropping funnel and argon protection, the magnetron was added successively, the above obtained dimethylmalonamide diacid (3g, 9mmol), 1,2-dichloroethane (30mL) , start stirring, and slowly add thionyl chloride (7.5 mL, 90 mmol) to the three-necked flask through a constant pressure dropping funnel at room temperature. After removing the solvent on a rotary evaporator, 2.8 g of a pale yellow solid powder (diamide diacid chloride 1) was obtained in a yield of 91%.

At room temperature and under argon protection, 2.5g (7.4mmol) of the above-mentioned solid (dimethylmalonamide dichloride) was added into a 100ml three-necked flask, dried dichloromethane (30mL) was added, and slowly dripped from a constant pressure dropping funnel Triethylamine (6.2 mL, 40 mmol) was added, 3,4-diaminopyridine (0.8 g, 7.4 mmol) was added in batches with stirring, the reaction was monitored by TLC until the raw materials disappeared, and the reaction was continued for 1 h. The solvent was removed on a rotary evaporator, water was added, vigorously stirred, suction filtered, the filtrate was rotary evaporated to dryness, and separated by column chromatography (gradient elution with methanol and dichloromethane) to obtain 2.4 g of the compound of formula II as a white powder with a yield of 85.0%.

Its hydrogen nuclear magnetic resonance spectrum is shown in Figure 4, which is completely consistent with Example 1.

Figure 5 is its carbon nuclear magnetic resonance spectrum, δ=174.00, 173.84, 173.81 and 172.19ppm are the peaks of four carbonyl carbons in the molecule respectively, δ=150.23, 147.86, 140.55, 124.76 and 117.39ppm are the five carbons on the pyridine ring The peaks of δ=58.51, 57.98 and 51.12ppm are the peaks of two aminoisobutyric acids on the intracyclic skeleton and the α carbons of one malonic acid structure, respectively, δ=25.71, 24.91 and 22.56ppm are the six methyl groups, respectively peak, confirming the structure of the target compound.

Figure 6 is a high-resolution mass spectrum, which is consistent with the mass spectrum of the product obtained in Example 1.

Example 3

The compound of formula II (200mg, 0.53mmol) and 60ml of dry dichloromethane were added to a 100ml flask under argon protection, and magnetic stirring was added at room temperature to disperse as evenly as possible in the solution to obtain a white suspension. Draw 1M KHMDS tetrahydrofuran solution (2.28ml, 2.28mmol) with a syringe, slowly add it to the system, the system immediately changes from a white suspension to an orange-yellow suspension, and after 1h, anhydrous ferric chloride solid (112mg, 0.692 mmol), the system immediately turned from orange to brownish black, stirred at room temperature overnight, and monitored by TLC until the reaction was complete. Suction filtration and wash the filter cake with a small amount of dichloromethane, the filter cake is dissolved in isopropanol, filtered, the obtained filtrate is placed on a rotary evaporator to evaporate the solvent, the solid is redissolved in water, filtered, and the filtrate is evaporated to dryness with a rotary evaporator, 220 mg of brown-yellow solid powder was obtained, the yield was 86%, and the melting point was higher than 280°C.

Figure 7 is a high-resolution electrospray mass spectrum.

The relative molecular weight of the expected target product is 466, and the (M-K) negatively charged peak of the target product is at the mass-to-charge ratio (m/z) 427 in the electrospray mass spectrum.

Accompanying drawing 8 is its infrared spectrogram.

Carbonyl peaks below 1700 cm ^-1 can be seen.

Example 4

According to the molar feeding amount, operation method and operation steps of Example 3, anhydrous ferric chloride was changed to anhydrous cobalt chloride (90mg, 0.692mmol), KHMDS tetrahydrofuran solution was changed to 1M LiHMDS tetrahydrofuran solution (2.28ml, 2.28 mmol), 210 mg of wine-red solid powder was obtained, the yield was 83%, and the melting point was higher than 280°C.

Figure 9 is a high-resolution electrospray mass spectrum.

The relative molecular weight of the expected target product is 469, and the (M-K) negative charge peak of the target product is at the mass-to-charge ratio (m/z) 430 in the electrospray mass spectrum.

Accompanying drawing 10 is its infrared spectrogram.

Carbonyl peaks below 1700 cm ^-1 can be seen.

Example 5

According to the molar feeding amount, operation method and operation steps of Example 3, the solvent was changed to 50 mL of anhydrous tetrahydrofuran, the anhydrous ferric chloride was changed to anhydrous copper acetate (126 mg, 0.692 mmol), and the KHMDS tetrahydrofuran solution was changed to tert-butyl Sodium alkoxide (220 mg, 2.28 mmol) to obtain 200 mg of wine-red solid powder, yield 80%, melting point greater than 280°C.

Figure 11 is a high-resolution electrospray mass spectrum.

The relative molecular weight of the expected target product is 473, and the (M-K) negatively charged peak of the target product is at the mass-to-charge ratio (m/z) 434 in the electrospray mass spectrum.

Accompanying drawing 12 is its infrared spectrogram.

Carbonyl peaks below 1700 cm ^-1 can be seen.

It should be noted that, in other embodiments, anhydrous copper acetate may be replaced with anhydrous copper chloride.

Example 6

According to the molar feeding amount, operation method and operation steps of Example 3, the solvent was changed to 50mL of anhydrous tetrahydrofuran, the anhydrous ferric chloride was changed to anhydrous manganese dichloride (88mg, 0.692mmol), and the KHMDS tetrahydrofuran solution was changed to 1M solution of potassium tert-butoxide in tetrahydrofuran (2.28 mg, 2.28 mmol) to obtain 190 mg of black solid powder, yield 75%, melting point greater than 280°C.

Figure 13 is a high-resolution electrospray mass spectrum.

The relative molecular weight of the expected target product is 465, and the (M-K) negatively charged peak of the target product is at the mass-to-charge ratio (m/z) 426 in the electrospray mass spectrum.

Figure 14 is its infrared spectrum.

Carbonyl peaks below 1700 cm ^-1 can be seen.

Example 7

In a stainless steel pressure-resistant reaction kettle (50 mL), add magnetron, 2-aminoisobutyric acid (2 g, 19.4 mmol), anhydrous pyridine (30 mL), diethyl dimethylmalonate (3.2 mL, 19.4 mmol) in turn mmol), close the reaction kettle after replacing the system with argon for 3 times, heat up to 200 ° C in an oil bath and maintain for 2 h, remove the reaction solution after cooling, remove pyridine on a rotary evaporator to obtain an oily substance, add 3 mol/L hydrochloric acid (10 mL) ) was adjusted to pH 2-3, a large amount of solid was precipitated, and after standing at low temperature for 1 h, suction filtration was performed, and the filter cake was washed three times with a small amount of acetonitrile to obtain a white solid powder that was dried and weighed 2.8 g, with a yield of 89%.

In a 100mL three-necked flask equipped with a constant pressure dropping funnel and argon protection, the magnetron was added successively, and the above obtained dimethylmalonamide diacid (2g, 6mmol), 1,2-dichloroethane (30mL) , start stirring, slowly add thionyl chloride (5 mL, 60 mmol) to the three-necked flask through a constant-pressure dropping funnel at room temperature, and then heat up to reflux after the dropwise addition, and stop the reaction after 8 h. After removing the solvent on a rotary evaporator, 1.9 g of a pale yellow solid powder (diamide diacid chloride 1) was obtained in a yield of 92%.

At room temperature and under argon protection, 1 g (3.0 mmol) of the above-mentioned solid (dimethylmalonamide diacid chloride) and ferric chloride (0.5 g, 3.0 mmol) were added to a 100 ml there-necked flask, and dry dichloromethane ( 15mL), triethylamine (2.5mL, 18mmol) was slowly added dropwise from a constant pressure dropping funnel, 3,4-diaminopyridine (0.37g, 3.0mmol) was added in batches under stirring, the reaction was followed by TLC, and the raw materials disappeared after 8h . After the reaction is over, filter and wash three times with 3*5ml ethanol. The filter cake was dissolved in isopropanol, filtered, the obtained filtrate was placed on a rotary evaporator to evaporate the solvent, the solid was redissolved in water, filtered, and the filtrate was evaporated to dryness with a rotary evaporator to obtain 1.1 g of brown-yellow solid powder with a yield of 1.1 g. 80.2%.

Figure 15 is a high-resolution electrospray mass spectrum of the compound of formula I (Fe) obtained by metal template method.

It is consistent with the mass spectrum (Fig. 7) of the compound obtained by the non-template method (Example 3).

Figure 16 is the infrared spectrum of the compound of formula I (Fe) obtained by the metal template method.

A carbonyl peak at a wavenumber of 1698 cm ^-1 can be seen.

The above characterization results are consistent with the non-template method product.

Example 8

In a stainless steel pressure-resistant autoclave (50 mL), add magnetron, 2-aminoisobutyric acid (1 g, 9.7 mmol), anhydrous pyridine (15 mL), diethyl difluoromalonate (1.6 mL, 9.7 mmol) in turn ), close the reaction kettle after replacing the system with argon for 3 times, heat up to 200°C in an oil bath and maintain it for 2h, remove the reaction solution after cooling, remove pyridine on a rotary evaporator to obtain an oily substance, add 3mol/L hydrochloric acid (5mL) The pH was adjusted to 2-3, and a large amount of solid was precipitated. After standing at low temperature for 1 hour, suction filtration was performed, and the filter cake was washed three times with a small amount of acetonitrile to obtain 2.5 g of white solid powder, which was dried and weighed, and the yield was 83%.

In a 100mL three-necked flask equipped with a constant pressure dropping funnel and argon protection, the magnetron was added successively, the above obtained difluoromalonamide diacid (2g, 6.4mmol), 1,2-dichloroethane (20mL) , start stirring, slowly add thionyl chloride (5 mL, 60 mmol) to the three-necked flask through a constant-pressure dropping funnel at room temperature, and then heat up to reflux after the dropwise addition, and stop the reaction after 8 h. After removing the solvent on a rotary evaporator, 2.1 g of a pale yellow solid (diamide diacid chloride 2) was obtained in a yield of 95%.

At room temperature and under argon protection, the obtained solid (difluoromalonamide diacid chloride) (2g, 5.7mmol), ferric chloride (0.92g, 5.7mmol) were added to a 100ml there-necked flask, and a dry two-necked flask was added. Chloromethane (30 mL) was slowly added dropwise with triethylamine (3 mL, 19 mmol) from a constant pressure dropping funnel, 3,4-diaminopyridine (0.62 g, 5.7 mmol) was added in batches under stirring, and the reaction was followed by TLC, after 6 h Raw materials disappear. After the reaction was completed, dichloromethane (30 mL) was added for filtration, and washed three times with 3*3 ml of ethanol. The filter cake was dissolved in isopropanol, filtered, the obtained filtrate was placed on a rotary evaporator to evaporate the solvent, the solid was redissolved in water, filtered, and the filtrate was evaporated to dryness with a rotary evaporator to obtain 2.5 g of black solid powder with a yield of 91.2 %.

FIG. 17 is a high-resolution mass spectrum of the fluorine-containing Fe complex of Example 8. FIG.

The relative molecular weight of the expected target product is 474, and the (M-K) negatively charged peak of the target product is at the mass-to-charge ratio (m/z) 435 in the electrospray mass spectrum.

Example 9

Using 2 mg of the compound of formula I obtained in Examples 3 to 6, 100 μL of hydrogen peroxide (30%), using water as a solvent (2 mL), and stirring the reaction for benzyl alcohol at 80° C. for 60 min, and calibrating benzyl alcohol and benzene by gas chromatography The amount of formaldehyde to determine the conversion and selectivity of the oxidation reaction.

Table 2 Oxidation results of p-benzyl alcohol with different catalysts in water solvent

As can be seen from the above table, the catalyst provided by the present application has a good effect on the catalytic oxidation of benzyl alcohol, and its conversion rate and selectivity are relatively high.

Similarly, the present application has also carried out experiments of catalytic oxidation of other alcohols to aldehydes, and catalytic oxidation of aldehydes to acid compounds, and the conversion rate and selectivity are both high.

In order to further prove the effect of the catalyst provided by the application in the catalytic oxidation reaction of alcohols and aldehyde compounds, the application has carried out experiments on the catalytic oxidation reaction under different solvent conditions, as follows:

Example 10

Use the Fe catalyst 2mg obtained in Example 3, 100 μL of hydrogen peroxide (30%), use different solvents (2mL) at 80° C. to stir the reaction for benzyl alcohol for 60min, and demarcate the amount of benzyl alcohol and benzaldehyde by gas chromatography, To determine the conversion and selectivity of the oxidation reaction.

Table 3 Oxidation results of p-benzyl alcohol under different solvents of Fe catalyst

As can be seen from the above table, in the presence of different solvents, the catalyst provided by the present application also has a good effect on the catalytic oxidation of benzyl alcohol.

Example 11

The pH was controlled at 7, the catalyst concentration was 2.5*10 ^-7 M, the hydrogen peroxide concentration was 2.5*10 ^-4 M, the dye concentration was 100 mg/L, and the temperature was 25 ℃, and the four cationic dyes were degraded for 30 minutes , use a COD meter to measure the COD value of the solution before (denoted as COD ₁ ) and after (denoted as COD _t ) respectively, and calculate the COD removal rate in 30min [(COD ₁ -COD _t )/COD ₁ ], as the catalyst Evaluation index of the dye removal effect. The data result is 4.

Table 4 COD removal rates of four cationic dyes oxidatively degraded for 30 min

As can be seen from the above table, the catalyst provided by the application has a good degrading effect on dye wastewater, and it can greatly reduce COD and reduce the pollution of wastewater to the environment within 30 minutes. Has application value.

The macrocyclic amide metal complex provided by the application has good catalytic effect, fast reaction speed, stable structure and high repeatable catalytic efficiency; it can be widely used in the catalytic oxidation reaction of organic compounds, especially the oxidation reaction of alcohol organic compounds and aldehyde organic compounds And in the degradation of dye wastewater, the chemical oxygen demand can be effectively reduced, and there is no secondary pollution.

Although specific embodiments of the present invention have been illustrated and described, it should be understood that various other changes and modifications can be made without departing from the spirit and scope of the invention. Therefore, it is intended that all such changes and modifications as fall within the scope of this invention be included in the appended claims.

Claims (3)

1. a preparation method of a macrocyclic amide metal complex, the structural formula of the macrocyclic amide metal complex is shown in formula I; Formula I: Wherein, R is CH ₃ or F, M is one of Fe, Co, Mn or Cu, M' is K, Na or Li; n=1 or 2; it is characterized in that the method comprises a first-stage reaction , the second-stage reaction and the third-stage reaction, The first stage reaction includes: A1. under inert gas atmosphere, in the system that 2-aminoisobutyric acid and anhydrous pyridine are formed, drip dimethylmalonyl chloride, after the reaction is finished, remove the solvent to obtain oil, and the oil is adjusted to pH to 2-3, suction filtration to obtain dimethylmalonamide diacid; or, A2. In an inert gas atmosphere, using anhydrous pyridine as a solvent, 2-aminoisobutyric acid and diethyl dimethyl malonate or diethyl difluoromalonate are heated and closed for reaction, and the solvent is removed after the reaction is completed To obtain an oily substance, adjust the pH of the oily substance to 2-3, and perform suction filtration to obtain dimethylmalonamide diacid or difluoromalonamide diacid; In the step A1, the reaction temperature is controlled to be 60-70°C, and the reaction time is 10-15h; in the step A2, the reaction temperature is controlled to be 180-240°C, and the reaction time is 1-3h; The second stage reaction includes: B. Under an inert gas atmosphere, add dimethylmalonamide diacid or difluoromalonamide diacid, anhydrous 1,2-dichloroethane to the reaction vessel successively, and then dropwise add dichloroethane The sulfoxide is heated to reflux after the dropwise addition, reacts for 6-10 h, and removes the solvent to obtain dimethylmalonamide dichloride or difluoromalonamide dichloride; The third stage reaction includes: C. Under an inert gas atmosphere, successively add the dimethylmalonamide dichloride or difluoromalonamide diacid chloride, anhydrous treated dichloromethane obtained in the above step B into the reaction vessel, and then dropwise add triethyl amine, at the same time, add 3,4-diaminopyridine in batches, remove the solvent after the reaction, then add water to vigorously stir, suction filtration, and use chromatographic column gradient elution to separate the filtrate after rotary evaporation to obtain the compound shown in formula II; chromatographic column elution The eluent used for separation is methanol and dichloromethane, and the volume ratio of methanol to dichloromethane in the eluent is 1:30-1:5; Formula II: R is _CH3 or F; D. Under an inert gas atmosphere, add the compound shown in formula II and the first solvent to the reaction vessel, then slowly add a strong base, after the reaction for 0.5-1.5h, add anhydrous metal salt, and stir the reaction at room temperature for 12-24h, The product shown in formula I is obtained through post-processing steps; Or a third-stage reaction consists of: E. under the protection of inert gas, the dimethylmalonamide dichloride or difluoromalonamide dichloride obtained in the above step B, the anhydrous metal salt are added in the reaction vessel, the second solvent is added, and then slowly dripped Triethylamine was added in batches with 3,4-diaminopyridine under stirring, and after the reaction for 6-10h, the product shown in formula I was obtained through the post-processing step; The first solvent is anhydrous dichloromethane or anhydrous THF, the second solvent is anhydrous pyridine or anhydrous dimethylformamide; the strong base is KHMDS, LiHMDS, tertiary Potassium butoxide or sodium tert-butoxide; The anhydrous metal salt is anhydrous ferric chloride, anhydrous cobalt chloride, anhydrous copper chloride, anhydrous copper acetate or anhydrous manganese dichloride. 2. method according to claim 1, is characterized in that, in described step D, post-processing step is specifically: The reaction system was suction filtered, the filter cake was washed with ethanol, then the filter cake was dissolved in isopropanol, and the filtrate was rotary evaporated to obtain a solid after filtration; The solid matter is dissolved in water, and after filtration, the filtrate is rotary evaporated to obtain the product shown in formula I. 3. The method according to any one of claims 1 and 2, characterized in that, in the step A1 or A2, after adjusting pH, suction filtration after standing for 1-2h, and the filter cake is washed with acetonitrile 2- 3 times.