CN116410191A - Compound with perylene imide and amide structures, and preparation method and application thereof - Google Patents

Abstract

The invention relates to the technical field of reversible photochromic materials, and discloses a compound with perylene imide and amide structures, a preparation method and application thereof. The compound provided by the present invention has the structure shown in formula (I), wherein, R ¹ and R ² are each independently selected from one of substituted or unsubstituted phenol, pyridine and furan, the phenol, pyridine and furan The substituent is selected from at least one of halogen, C1-C4 alkyl, C1-C4 alkoxy, nitro and amino; R ³ , R ⁴ , R ⁵ and R ⁶ are each independently halogen, C1-C4 C4 alkyl or C1-C4 alkoxy. Under the action of ultraviolet light, the compound with peryleneimide and amide structure provided by the present invention can obtain energy to undergo proton transition, and its color can change in solid state and solution state, and the compound with peryleneimide and amide structure provided by the present invention There are hydrogen bonds in the molecule in the compound structure of the structure, and it belongs to a molecule with a large conjugated structure, which makes its structure unique and stable.

Description

Compounds with perylene imide and amide structures and their preparation methods and applications

technical field

The invention relates to the technical field of reversible photochromic materials, in particular to a compound with a perylene imide and amide structure and a preparation method and application thereof.

Background technique

Photochromism means that the molecular structure of certain compounds will change under the action of light of a certain wavelength and intensity, resulting in a change in the peak absorption of light, that is, a corresponding change in color, and this change is generally reversible. As a new type of intelligent material, photochromic materials can be applied in the fields of optical information storage, anti-counterfeiting materials, decoration and national defense. Therefore, photochromic materials have gradually become a research hotspot. The photochromism of organic systems is often accompanied by many processes related to photochemical reactions, resulting in a certain change in molecular structure. The reaction methods mainly include: valence bond isomerization, cis-trans isomerization, bond breaking, polymerization , oxidation-reduction, pericyclic reactions, etc. Organic photochromic materials with ketene-type valence bond isomerization have been widely studied and used, but the isomerization of amine hydrogen and carbonyl group leads to less research on photochromic materials.

Current studies have shown that the photochromism of perylene anhydride derivatives mainly lies in the modification of groups with reversible bond breaks, such as diarylethene, but the photochromic materials synthesized by this method are limited in use and cannot be prepared in a solid state The following photochromic materials cannot be used as a basis to produce diversified commodities.

In summary, organic compounds can be used to construct functional optical materials. Although there are many studies on photochromic compounds, there are few reports on the photochromic derivatives obtained from the reaction of aromatic hydrazides and perylene anhydrides in solid and solution states.

Contents of the invention

In view of the above-mentioned problems in the prior art, the object of the present invention is to provide a compound having a perylene imide and amide structure, its preparation method and application. The compounds with perylene imide and amide structures provided by the invention have photochromic properties both in solid state and in solution state.

The first aspect of the present invention provides a compound having a perylene imide and amide structure, the compound has a structure shown in formula (I):

Wherein, ^R1 and ^R2 are each independently selected from one of substituted or unsubstituted phenol, pyridine and furan, and the substituents of said phenol, pyridine and furan are selected from halogen, C1-C4 alkyl, C1- At least one of C4 alkoxy, nitro and amino;

R ³ , R ⁴ , R ⁵ and R ⁶ are each independently halogen, C1-C4 alkyl or C1-C4 alkoxy.

The second aspect of the present invention provides a method for preparing a compound having a perylene imide and amide structure, the method comprising: in the presence of imidazole, contacting the perylene anhydride represented by formula (II) with an aromatic hydrazide compound,

Wherein, in formula (II), R ³ , R ⁴ , R ⁵ and R ⁶ are each independently halogen, C1-C4 alkyl or C1-C4 alkyl.

The third aspect of the present invention provides an application of the compound having a peryleneimide and amide structure described in the first aspect or the method described in the second aspect in the preparation of a reversible photochromic smart material.

Compared with prior art, the beneficial effect of the present invention:

Under the action of ultraviolet light, the compound with perylene imide and amide structure obtained by the present invention obtains energy and undergoes proton transition, and its color can change in both solid state and solution state, and the present invention The compounds with perylene imide and amide structures provided by the invention have hydrogen bonds in the molecules and belong to molecules with large conjugated structures, making the structures unique and stable. In addition, the present invention obtains a compound with photochromic properties by reacting the hydrazinolysis product of aromatic ester compound with perylene anhydride, the process is simple and easy to operate, that is, the modification of simple compound (such as through the reaction of perylene anhydride and aromatic hydrazide) The photochromic effect can be achieved, and the preparation cost can be greatly reduced compared with complex modification methods.

Description of drawings

Fig. 1 is the perylene imide-amide proton nuclear magnetic resonance spectrogram that embodiment 1 prepares;

Among Fig. 2 A) is the variation graph of the ultraviolet absorption spectrum of the compound prepared in Example 1 under the ultraviolet light irradiation of wavelength 365nm with the irradiation time; B) is the ultraviolet light of the compound prepared in Example 1 under the ultraviolet light of wavelength 365nm in Fig. 1 Variation curve of fluorescence emission spectrum with irradiation time under irradiation;

Fig. 3 is a graph showing the color development effect of the compound solid photochromic material prepared in Example 1 before and after irradiation with ultraviolet light with a wavelength of 365nm.

Detailed ways

Neither the endpoints nor any values of the ranges disclosed herein are limited to such precise ranges or values, and these ranges or values are understood to include values approaching these ranges or values. For numerical ranges, between the endpoints of each range, between the endpoints of each range and individual point values, and between individual point values can be combined with each other to obtain one or more new numerical ranges, these values Ranges should be considered as specifically disclosed herein.

The first aspect of the present invention provides a compound having a perylene imide and amide structure, the compound has a structure shown in formula (I):

Wherein, R ¹ and R ² are each independently selected from one of substituted or unsubstituted phenol, pyridine and furan, and the substituents of said phenol, pyridine and furan are selected from halogen, C1-C4 alkyl (methyl , ethyl, n-propyl, isopropyl, n-butyl, isobutyl or tert-butyl), C1-C4 alkoxy (methoxy, ethoxy, n-propoxy, isopropoxy , n-butoxy, isobutoxy or tert-butoxy), nitro and amino at least one;

R ³ , R ⁴ , R ⁵ and R ⁶ are each independently halogen, C1-C4 alkyl or C1-C4 alkoxy.

According to some embodiments of the present invention, R ¹ and R ² are each independently selected from one of phenol, pyridine and furan.

According to some embodiments of the present invention, R ³ , R ⁴ , R ⁵ and R ⁶ are all halogen.

According to some embodiments of the present invention, the halogen is Br or Cl.

Specifically, R ¹ and R ² can each be independently selected from any one of the following groups:

表示可以与其他原子或基团以共价键的方式连接。in

Indicates that it can be covalently linked to other atoms or groups.

The second aspect of the present invention provides a method for preparing a compound having a perylene imide and amide structure, the method comprising: in the presence of imidazole, carrying out a perylene anhydride compound represented by formula (II) with an aromatic hydrazide compound Contact, obtain the compound shown in formula (I),

Wherein, in formula (II), R ³ , R ⁴ , R ⁵ and R ⁶ are each independently selected from halogen, C1-C4 alkyl or C1-C4 alkyl.

According to some embodiments of the present invention, R ¹ and R ² are each independently selected from one of phenol, pyridine and furan.

In the present invention, preferably, the perylene anhydride shown in formula (II) is selected from the structures shown in formula (II-1) or formula (II-2):

According to some embodiments of the present invention, the contacting conditions may include: a temperature of 80-200°C (80°C, 90°C, 100°C, 110°C, 120°C, 130°C, 140°C, 150°C, 160°C, 170°C, 180°C, 190°C, 200°C or any value between the above values), preferably 80-160°C, for 2-10 hours.

In order to make the reaction better, the molar ratio of the perylene anhydride compounds, aromatic hydrazide compounds and imidazoles shown in formula (II) has certain restrictions, for example, the molar ratio of the perylene anhydrides, aromatic hydrazide compounds and imidazoles The ratio may be 1:(1-5):(20-35), preferably 1:(2-3):(25-30).

According to some embodiments of the present invention, the contacting is performed in the presence of a first solvent, and the first solvent is selected from at least one of C1-C4 saturated monoalcohols, DMF and NMP.

The present invention has no special limitation on the amount of the first solvent, and it is sufficient to meet the requirements of the present invention. For example, with respect to 1 g of the perylene anhydride compound represented by formula (II), the amount of the first solvent used is 20-40mL.

According to some embodiments of the present invention, the aromatic hydrazide compound is selected from one of substituted or unsubstituted hydroxybenzoic hydrazides, picolinic hydrazides and furoyl hydrazides, and the hydroxybenzoic hydrazide, The substituents of picolinyl hydrazide and furoyl hydrazide are at least one of halogen, C1-C4 alkyl, C1-C4 alkoxy, nitro and amino.

Preferably, the aromatic hydrazide compound is selected from one of the following groups:

The present invention has no special limitation on the post-treatment of the reaction of the perylene anhydride shown in formula (II) and the aromatic hydrazide compound, which can be carried out in the following manner: the system after the reaction is lowered to room temperature, washed and centrifuged with deionized water, and Wash and centrifuge with alkali (such as 10-30wt% potassium bicarbonate aqueous solution), deionized water in sequence, and finally dry to obtain the compound with the structure shown in formula (I). There are no special restrictions on the amount of alkali and deionized water used for washing, the conditions of centrifugation, etc., as long as the requirements of the present invention can be met.

According to some embodiments of the present invention, the aromatic hydrazide compound is obtained by reacting an aromatic ester compound with hydrazine hydrate.

According to some embodiments of the present invention, the reaction temperature of the aromatic ester compound and hydrazine hydrate is 50-100°C (50°C, 60°C, 70°C, 80°C, 90°C, 100°C or any value between the above values. value), the time is 2-10h.

According to some embodiments of the present invention, the molar ratio of the aromatic ester compound to hydrazine hydrate is 1:(10-30).

According to some embodiments of the present invention, the aromatic ester compound is selected from one of substituted or unsubstituted methyl hydroxybenzoate, methyl picolinate and methyl furoate, and the methyl hydroxybenzoate, The substituents of methyl picolinate and methyl furoate are selected from at least one of halogen, C1-C4 alkyl, C1-C4 alkoxy, nitro and amino.

In the present invention, the reaction between the aromatic ester compound and hydrazine hydrate is carried out in the presence of a second solvent, and the second solvent is selected from at least one of C1-C4 saturated monohydric alcohol, DMF and NMP.

The post-treatment of the reaction of aromatic ester compounds and hydrazine hydrate is not particularly limited in the present invention, and can be carried out in the following manner: the reacted system is cooled to room temperature, and the aromatic hydrazide compound can be obtained by suction filtration.

In the present invention, the first solvent and the second solvent may be the same or different.

The third aspect of the present invention provides an application of the compound having a peryleneimide and amide structure described in the first aspect or the method described in the second aspect in the preparation of a reversible photochromic smart material.

The present invention will be described in detail below by way of examples.

In the following examples, unless otherwise specified, the raw materials, solvents, catalysts and bases used are all commercially available.

Wherein, the yield (molar yield) is calculated by actual yield/theoretical yield×100%. Purity was determined by proton NMR spectroscopy.

Example 1

(1) Add 1g of methyl salicylate, 5g of hydrazine hydrate and 20mL of ethanol successively in a 100mL round-bottomed flask, reflux (70°C) under _N2 atmosphere, cool to room temperature and suction filter to obtain solid (salicylhydrazide), yield 85%;

(2) Add 0.27g (0.51mmol) of perylene anhydride compound represented by formula (II-2), 0.17g of salicylhydrazide, 1g of imidazole and 6mL of absolute ethanol to a 25mL Stocke bottle, and react at 120°C under nitrogen protection After 7h, the reacted mixture was cooled to room temperature and poured into 100mL deionized water for washing and centrifugation, followed by washing with 50mL potassium bicarbonate solution (concentration of 20wt%) and 100mL deionized water successively, and the centrifuged solid (red) obtained at 50 °C and vacuum-dried to obtain the compound represented by formula (I) with a purity of 90 wt% and a yield of 75%. The compound represented by the obtained formula (I) (the compound having perylene imide and amide structure) is subjected to proton nuclear magnetic spectrum testing, and the proton nuclear magnetic resonance spectrum is shown in FIG. 1 .

R³、R⁴、R⁵和R⁶均为Cl。In formula (I), R ¹ and R ² are

R ³ , R ⁴ , R ⁵ and R ⁶ are all Cl.

Example 2

(1) Add 1g of methyl m-hydroxybenzoate, 5g of hydrazine hydrate and 20mL of ethanol successively to a 100mL round-bottomed flask, reflux (70°C) under _N2 atmosphere, cool to room temperature and suction filter to obtain a solid (m-hydroxybenzoate Hydrazide), the yield is 83%;

(2) Add 0.27g (0.51mmol) of perylene anhydride compounds represented by formula (II-2), 0.17g of m-hydroxybenzoic hydrazide, 1g of imidazole and 6mL of absolute ethanol to a 25mL Stocke bottle successively, under nitrogen protection React at 120°C for 7h, pour the reacted mixture into 100mL deionized water after cooling to room temperature, wash and centrifuge, then wash with potassium bicarbonate solution and deionized water successively, and dry the solid obtained by centrifugation in vacuum at 50°C to obtain the formula (I ) The compound shown in ) has a purity of 88wt% and a yield of 75%.

R³、R⁴、R⁵和R⁶均为Cl。In formula (I), R ¹ and R ² are

R ³ , R ⁴ , R ⁵ and R ⁶ are all Cl.

Example 3

(1) Add 1g of methyl p-hydroxybenzoate, 5g of hydrazine hydrate and 20mL of ethanol successively to a 100mL round bottom flask, reflux (70°C) under _N2 atmosphere, cool to room temperature and suction filter to obtain a solid (p-hydroxybenzoyl Hydrazine), yield is 80%;

(2) Add 0.27g (0.51mmol) of perylene anhydride compounds represented by formula (II-2), 0.17g of p-hydroxybenzoic hydrazide, 1g of imidazole and 6mL of absolute ethanol to a 25mL Stocke bottle successively, under nitrogen protection React at 120°C for 7h, pour the reacted mixture into 100mL deionized water after cooling to room temperature, wash and centrifuge, then wash with potassium bicarbonate solution and deionized water successively, and dry the solid obtained by centrifugation in vacuum at 50°C to obtain the formula (I ) shown in the compound, the yield was 72%.

R³、R⁴、R⁵和R⁶均为Cl。In formula (I), R ¹ and R ² are

R ³ , R ⁴ , R ⁵ and R ⁶ are all Cl.

Example 4

(1) Add 1g of methyl 2-picolinate, 5g of hydrazine hydrate and 20mL of ethanol successively to a 100mL round bottom flask, reflux (70°C) under _N2 atmosphere, cool to room temperature and suction filter the obtained solid (2-pyridine Formic hydrazide), the yield is 80%;

(2) Add 0.27g (0.51mmol) of perylene anhydride compounds represented by formula (II-2), 0.16g of 2-pyridinecarbohydrazide, 1g of imidazole and 6mL of absolute ethanol to a 25mL Stocke bottle successively, under nitrogen protection Reaction at 120°C for 8h, the reacted mixture was cooled to room temperature and then poured into 100mL deionized water for washing and centrifugation, followed by washing with potassium bicarbonate solution and deionized water successively, and the solid obtained by centrifugation was vacuum-dried at 50°C to obtain the formula ( The compound shown in I) has a purity of 89% by weight and a yield of 75%.

R³、R⁴、R⁵和R⁶均为Cl。In formula (I), R ¹ and R ² are

R ³ , R ⁴ , R ⁵ and R ⁶ are all Cl.

Example 5

(1) Add 1g of methyl 2-furancarboxylate, 5g of hydrazine hydrate and 20mL of ethanol successively to a 100mL round-bottomed flask, reflux (70°C) under _N2 atmosphere, cool to room temperature and suction filter to obtain a solid (2-furanformyl Hydrazide), the productive rate is 75%;

(2) Add 0.27g (0.51mmol) of perylene anhydride compounds represented by formula (II-2), 0.15g of 2-furan hydrazide, 1g of imidazole and 6mL of absolute ethanol to a 25mL Stocke bottle successively, under nitrogen protection Reaction at 120°C for 8h, the reacted mixture was cooled to room temperature, poured into 100mL deionized water, washed and centrifuged, then washed with potassium bicarbonate solution and deionized water in sequence, and the solid obtained by centrifugation was vacuum-dried at 50°C to obtain formula (I) The compound shown has a purity of 90% by weight and a yield of 76%.

R³、R⁴、R⁵和R⁶均为Cl。In formula (I), R ¹ and R ² are

R ³ , R ⁴ , R ⁵ and R ⁶ are all Cl.

Comparative example 1

(1) In a 100mL round bottom flask, add 1g of salicylaldehyde, 5g of hydrazine hydrate and 20mL of ethanol successively under _N Atmosphere reflux (70°C), cool to room temperature and suction filter to obtain solid (salicylaldehyde hydrazinolysis product), product The rate is 85%;

(2) Add 0.27g (0.51mmol) of perylene anhydride compounds shown in formula (II-2), 0.17g of salicylaldehyde hydrazinolysis product, 1g of imidazole and 6mL of absolute ethanol successively to a 25mL Stocke bottle, under nitrogen protection, 120 ℃ for 8 hours, the reacted mixture was cooled to room temperature, poured into 100mL deionized water, washed and centrifuged, then washed with potassium bicarbonate solution and deionized water in sequence, and the solid obtained by centrifugation was dried in vacuum at 50℃ to obtain imide-amide The compound has a purity of 85% by weight and a yield of 79%.

The compounds obtained from the above comparative examples have no color change before and after exposure to light, and do not have photochromic properties.

test case 1

The compound represented by the formula (I) prepared in the above-mentioned Example 1 was formulated into a 1×10 ^-5 mol/L DMF solution, and 1 mL of the solution was irradiated with a 365 nm ultraviolet lamp under stirring and observed, and then the solution was placed in a N ₂ atmosphere Heat to 150°C and stir for 10 min. Under the ultraviolet light irradiation of wavelength 365nm of the compound prepared in the solution state, the UV absorption spectrum varies with the irradiation time (see Figure 2) and the fluorescence emission spectrum varies with the irradiation time under the ultraviolet light irradiation of the wavelength 365nm change curve (see Figure 3). It can be seen from Figure 2 that with the prolongation of the illumination time, the intensity of the ultraviolet absorption peak at 400nm wavelength is gradually enhanced, and the intensity of the ultraviolet absorption peak at 480nm and 525nm wavelength is gradually weakened; The fluorescence emission intensity at the wavelength gradually decreases. The results show that the structure of the peryleneimide-amide of the formula (I) changes in the solution state, and has photochromic properties.

Evenly stain the film of the compound shown in the formula (I) that above-mentioned embodiment 1 obtains, be covered with the black cardboard of sun or flower petal shape, under the ultraviolet light irradiation of wavelength 365nm 20min; Obtain the color development effect of solid photochromic material Figure (see Fig. 3), the result of Fig. 3 shows that the compound with perylene imide and amide structure shown in the formula (I) prepared in Example 1 has photochromic properties in solid state.

Tested in the above manner, the compounds having peryleneimide and amide structures represented by formula (I) prepared in Examples 2-5 also have photochromic properties in solution or solid state.

The preferred embodiments of the present invention have been described in detail above, however, the present invention is not limited thereto. Within the scope of the technical concept of the present invention, various simple modifications can be made to the technical solution of the present invention, including the combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be regarded as the disclosed content of the present invention. All belong to the protection scope of the present invention.

Claims (10)

1. A compound having perylene imide and amide structures, characterized in that the compound has a structure represented by formula (I):

wherein R is ¹ And R is ² Each independently selected from one of a substituted or unsubstituted phenol, pyridine and furan, the substituents of the phenol, pyridine and furan being selected from at least one of halogen, C1-C4 alkyl, C1-C4 alkoxy, nitro and amino;

R ³ 、R ⁴ 、R ⁵ and R is ⁶ Each independently is halogen, C1-C4 alkyl or C1-C4 alkoxy.

2. The compound of claim 1, wherein R ¹ And R is ² Each independently selected from one of phenol, pyridine and furan;

R ³ 、R ⁴ 、R ⁵ and R is ⁶ All are halogen;

preferably, the halogen is Br or Cl.

3. A process for preparing a compound having a perylene imide and amide structure, the process comprising: in the presence of imidazole, perylene anhydride compounds shown in a formula (II) are contacted with aromatic hydrazide compounds,

wherein in formula (II), R ³ 、R ⁴ 、R ⁵ And R is ⁶ Each independently is halogen, C1-C4 alkyl or C1-C4 alkyl.

4. A method according to claim 3, wherein R ³ 、R ⁴ 、R ⁵ And R is ⁶ All are halogen;

preferably, the halogen is Br or Cl.

5. The method of claim 3 or 4, wherein the contacting conditions comprise: the temperature is 80-160 ℃ and the time is 2-10h.

6. The method according to claim 3 or 4, wherein the molar ratio of the perylene anhydride compound, the aromatic hydrazide compound and the imidazole represented by formula (II) is 1: (1-5): (20-35), preferably 1: (2-3): (25-30);

and/or the contacting is performed in the presence of a first solvent, and the first solvent is selected from at least one of a C1-C4 saturated monohydric alcohol, DMF, and NMP;

preferably, the first solvent is used in an amount of 20 to 40mL relative to 1g of the perylene anhydride compound represented by formula (II).

7. The method according to claim 4 or 5, wherein the aromatic hydrazide compound is selected from one of substituted or unsubstituted hydroxybenzohydrazines, pyridine hydrazides, and furan hydrazides, the substituents of which are selected from at least one of halogen, C1-C4 alkyl, C1-C4 alkoxy, nitro, and amino;

preferably, the aromatic hydrazide compound is selected from one of the following groups:

8. the method according to claim 7, wherein the aromatic hydrazide compound is obtained by reacting an aromatic ester compound with hydrazine hydrate.

9. The method of claim 8, wherein the reaction of the aromatic ester compound with hydrazine hydrate is carried out at a temperature of 50-100 ℃ for a time of 2-10 hours;

and/or the molar ratio of the aromatic ester compound to the hydrazine hydrate is 1: (10-30);

and/or the aromatic ester compound is selected from one of substituted or unsubstituted methyl hydroxybenzoate, methyl picolinate and methyl furancarboxylate, and the substituent of the methyl hydroxybenzoate, methyl picolinate and methyl furancarboxylate is selected from at least one of halogen, C1-C4 alkyl, C1-C4 alkoxy, nitro and amino.

10. Use of a compound having a perylene imide and amide structure as defined in claim 1 or 2 or a method as defined in any of claims 3-9 for the preparation of a reversible photochromic smart material.

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