阅读说明：本技术 一种异喹啉酮-芳酰肼衍生物及其制备方法 (Isoquinolinone-aroylhydrazide derivative and preparation method thereof ) 是由 黄小波 王丹 雷云祥 刘妙昌 吴华悦 于 2021-08-06 设计创作，主要内容包括：本发发明设计合成了一种异喹啉酮-芳酰肼衍生物及其制备方法,得到了一个1位肼基的异喹啉酮衍生物,氨基与羰基相邻,因此除酮-烯醇互变异构外,还存在一种酮型结构和两种烯醇型结构。本发明通过改变芳基来调节目标化合物的光物理性质,这些化合物表现出固态荧光,其波长覆盖了从蓝色到红色的整个可见光,具有全波长可调发射光谱。(The invention designs and synthesizes the isoquinolinone-aroylhydrazide derivative and the preparation method thereof, and obtains the isoquinolinone derivative with 1-site hydrazino, and the amino is adjacent to the carbonyl, so that a ketone type structure and two enol type structures exist besides ketone-enol tautomerism. The present invention adjusts the photophysical properties of target compounds by changing the aryl groups, and these compounds exhibit solid state fluorescence with wavelengths that cover the entire visible spectrum from blue to red, with a full wavelength tunable emission spectrum.)

1. An isoquinolinone-aroylhydrazide derivative characterized by:

the molecular formula is as follows:

wherein Ar is

2. An isoquinolinone-aroylhydrazide derivative according to claim 1, wherein:

is prepared by the reaction of a compound A, 4-methyl carboxylate, hydrazine hydrate and aromatic aldehyde;

the molecular formula of the compound A is as follows:

3. an isoquinolinone-aroylhydrazide derivative according to claim 2, wherein:

the aromatic aldehyde is:

4. a process for the preparation of any isoquinolinone-aroylhydrazide derivatives as claimed in claims 1 to 3, characterized in that:

the method comprises the following steps:

the molecular formula isMixing the compound A and 4-methyl carboxylate in a solvent A for reaction to obtain a compound B;

step two: mixing the compound B and hydrazine hydrate in a solvent B for reaction to obtain a compound C;

step three: and mixing the compound C and aromatic aldehyde in a solvent C for reaction to obtain the isoquinolone derivative.

5. The method for producing an isoquinolinone-aroylhydrazide derivative according to claim 4, wherein: the solvent A is CH₃CN。

6. The method for producing an isoquinolinone-aroylhydrazide derivative according to claim 4, wherein: the solvent B is ethyl acetate.

7. The method of claim 4, wherein:

the solvent C is DMF.

8. The method for producing an isoquinolinone-aroylhydrazide derivative according to claim 4, wherein: in the first step, a mixture of the compound A, 4-methyl carboxylate and the solvent A is stirred at 90 ℃ for 5 hours, cooled to room temperature, filtered and concentrated under reduced pressure, and purified by column chromatography on silica gel to obtain the compound B.

9. The method for producing an isoquinolinone-aroylhydrazide derivative according to claim 4, wherein: and in the second step, the mixture of the compound B, hydrazine hydrate and the solvent B is stirred for 8 hours at the temperature of 80 ℃, and after the mixture is cooled to room temperature, the mixture is poured into methanol to precipitate a crude product. The crude product was washed 5 times with methanol and then dried to give pure title compound C.

10. The method for producing an isoquinolinone-aroylhydrazide derivative according to claim 4, wherein: and in the third step, the mixture of the compound C, the aromatic aldehyde and the solvent C is stirred for 12 hours at the temperature of 120 ℃, after the mixture is cooled to room temperature, the mixture is poured into methanol and stirred for 2 hours, a crude product is separated out, the crude product is washed with the methanol for three times, and then the obtained product is dried to obtain the isoquinolone derivative.

Technical Field

The invention relates to the field of macromolecules, in particular to an isoquinolone-aroylhydrazide derivative and a preparation method thereof.

Background

The solid fluorescent stimulus responsive material is widely concerned about potential application in the aspects of sensors, information storage, anti-counterfeiting materials and the like. The change in fluorescence color of these materials, which are considered to be the main response signals, is often the result of morphological changes through the modification of molecular conformation, intermolecular interactions and packing arrangements under external stimuli such as pressure, heat or organic vapors. The behavior of piezochromic (MFC) often results from a transition between different crystal structures or from a crystalline state to an amorphous state. Polymorphism is a very common phenomenon, but the difficulty is that obtaining polymorphic substances that emit different fluorescence strongly depends on experimental experience, and therefore, it is of positive interest to develop new acquisition modes based on single molecules. Isoquinoline is an excellent fluorescent material structural unit. However, pure organic isoquinolines with solid-state fluorescence have been rarely reported, probably because the rigid planar structure of the isoquinoline ring easily leads to an aggregate quenching (ACQ) effect. .

Disclosure of Invention

Aiming at the defects in the prior art, the invention aims to provide an isoquinolone-aroylhydrazide derivative which is not easy to aggregate and quench effect and a preparation method thereof.

In order to achieve the purpose, the invention provides the following technical scheme:

an isoquinolone derivative, a process for its preparation,

the molecular formula is as follows:

wherein Ar is

As a further improvement of the present invention,

is prepared by the reaction of a compound A, 4-methyl piperidine formate, hydrazine hydrate and aromatic aldehyde;

the molecular formula of the compound A is as follows:

as a further improvement of the present invention,

the aromatic aldehyde is:

as a further improvement of the present invention,

the method comprises the following steps:

the molecular formula isMixing the compound A and 4-methyl piperidine formate in a solvent A for reaction to obtain a compound B;

step two: mixing the compound B and hydrazine hydrate in a solvent B for reaction to obtain a compound C;

step three: and mixing the compound C and aromatic aldehyde in a solvent C for reaction to obtain the isoquinolone derivative.

As a further improvement of the present invention,

the solvent A is CH₃CN。

As a further improvement of the present invention,

the solvent B is ethyl acetate.

As a further improvement of the present invention,

the solvent C is DMF.

As a further improvement of the present invention,

in the first step, a mixture of the compound A, methyl 4-piperidinecarboxylate and the solvent A is stirred at 90 ℃ for 5 hours, cooled to room temperature, filtered and concentrated under reduced pressure, and purified by column chromatography on silica gel to obtain the compound B.

As a further improvement of the present invention,

and in the second step, the mixture of the compound B, hydrazine hydrate and the solvent B is stirred for 8 hours at the temperature of 80 ℃, and after the mixture is cooled to room temperature, the mixture is poured into methanol to precipitate a crude product. The crude product was washed 5 times with methanol and then dried to give pure title compound C.

As a further improvement of the present invention,

and in the third step, the mixture of the compound C, the aromatic aldehyde and the solvent C is stirred for 12 hours at the temperature of 120 ℃, after the mixture is cooled to room temperature, the mixture is poured into methanol and stirred for 2 hours, a crude product is separated out, the crude product is washed with the methanol for three times, and then the obtained product is dried to obtain the isoquinolone derivative.

The reaction equation of the isoquinolone derivative prepared by the invention is as follows:

the invention designs and synthesizes 1-amino isoquinoline derivative to react with hydrazine hydrate to obtain 1-hydrazino isoquinoline ketone derivative, and amino is adjacent to carbonyl, so that a ketone structure and two enol structures exist besides keto-enol tautomerism. The present invention adjusts the photophysical properties of target compounds by changing the aryl groups, and these compounds exhibit solid state fluorescence with wavelengths that cover the entire visible spectrum from blue to red, with a full wavelength tunable emission spectrum.

Drawings

FIG. 1 is a schematic diagram showing the structure conversion of BHIQ of a compound in example 1 of the present invention;

FIG. 2 is a schematic diagram of structure conversion of compound NHIQ in example 2 of the present invention;

FIG. 3 is a schematic diagram of the structure conversion of the compound AHIQ in example 3 of the present invention;

FIG. 4 is a schematic diagram showing structural transition of compound TPHIQ in example 4 of the present invention;

FIG. 5 is a UV emission spectrum of a compound liquid obtained in examples 1 to 4 of the present invention;

FIG. 6 is a fluorescence emission spectrum of the compound liquids obtained in examples 1 to 4 of the present invention;

FIG. 7 is an XRD plot of the BHIQ-ms form of the compound BHIQ obtained in example 1 of the present invention under different conditions;

FIG. 8 is an XRD plot of the BHIQ-g form of the compound BHIQ obtained in example 1 of the present invention under different conditions;

FIG. 9 is an XRD curve of the BHIQ-g form of the compound BHIQ obtained in example 1 of the present invention under natural time variation;

FIG. 10 is XRD curves of NHIQ-sb form of compound NHIQ obtained in example 2 of the present invention under different conditions;

FIG. 11 is a fluorescence emission spectrum of NHIQ-sb form of compound NHIQ obtained in example 2 according to the present invention under different conditions;

FIG. 12 is a fluorescence emission spectrum of NHIQ-g form of compound NHIQ obtained in example 2 according to the present invention under different conditions;

FIG. 13 is XRD curves under different conditions for NHIQ-g form of compound NHIQ obtained in example 2 of the present invention;

FIG. 14 is a fluorescence emission spectrum of the AHIQ-o form of the compound AHIQ obtained in example 3 of the present invention under different conditions;

FIG. 15 is an XRD plot of the AHIQ-o form of the compound AHIQ obtained in example 3 of the present invention under different conditions;

FIG. 16 is a fluorescence emission spectrum of the AHIQ-r form of the compound AHIQ obtained in example 3 of the present invention under different conditions;

FIG. 17 is an XRD plot of the AHIQ-r form of the compound AHIQ obtained in example 3 of the present invention under different conditions;

FIG. 18 is a fluorescence emission spectrum of compound TPHIQ obtained in example 4 of the present invention under different conditions;

FIG. 19 is an XRD profile for compound TPHIQ obtained in example 4 of the present invention under different conditions;

FIG. 20 shows BHIQ as a compound in example 1 of the present invention¹H NMR (DMSO-d6, 500MHz) spectrum;

FIG. 21 shows BHIQ as a compound in example 1 of the present invention¹³C NMR(DMSO-d₆500MHz) spectrum;

FIG. 22 shows the reaction scheme of NHIQ in example 2¹H NMR (DMSO-d6, 500MHz) spectrum;

FIG. 23 shows the reaction scheme of compound NHIQ in example 2 of the present invention¹³C NMR(DMSO-d₆500MHz) spectrum; .

FIG. 24 shows AHIQ as a compound in example 3 of the present invention¹H NMR (DMSO-d6, 500MHz) spectrum;

FIG. 25 shows AHIQ as a compound in example 3 of the present invention¹³C NMR(DMSO-d₆500MHz) spectrum;

FIG. 26 is a drawing showing TPHIQ, a compound in example 4 of the present invention¹H NMR (DMSO-d6, 500MHz) spectrum;

FIG. 27 is a drawing showing TPHIQ, a compound in example 4 of the present invention¹³C NMR(DMSO-d₆500MHz) spectrum.

Detailed Description

The invention will be further described in detail with reference to the following examples, which are given in the accompanying drawings.

Example 1:

the molecular formula isCompound A of (2.0g, 9.3mmol), methyl 4-piperidinecarboxylate (18mmol) and CH₃CN (15mL) mixture was stirred at 90 ℃ for 5h, cooled to room temperature, and the reaction mixture was concentrated by filtration under reduced pressure. Purification by column chromatography on silica gel gave compound B.

A mixture of Compound B (2.5g, 7.5mmol), hydrazine hydrate (15mL) and ethyl acetate (15mL) was stirred at 80 ℃ for 8h, after cooling to room temperature, the mixture was poured into methanol (100mL) to precipitate the crude product. The crude product was washed 5 times with methanol and then dried to give pure title compound C.

Compound C (1.5g, 6.5mmol) of formulaThe mixture of aromatic aldehyde (12mmol) and DMF (15mL) was stirred at 120 ℃ for 12h, cooled to room temperature, and then the mixture was poured into methanol (200mL) and stirred for 2h to isolate the crude product. The crude product was washed three times with methanol and then dried to give pure target compound BHIQ.

Example 2:

a molecule is preparedIs of the formulaCompound A of (2.0g, 9.3mmol), methyl 4-piperidinecarboxylate (18mmol) and CH₃CN (15mL) mixture was stirred at 90 ℃ for 5h, cooled to room temperature, and the reaction mixture was concentrated by filtration under reduced pressure. Purification by column chromatography on silica gel gave compound B.

A mixture of Compound B (2.5g, 7.5mmol), hydrazine hydrate (15mL) and ethyl acetate (15mL) was stirred at 80 ℃ for 8h, after cooling to room temperature, the mixture was poured into methanol (100mL) to precipitate the crude product. The crude product was washed 5 times with methanol and then dried to give pure title compound C.

Compound C (1.5g, 6.5mmol) of formulaThe mixture of aromatic aldehyde (12mmol) and DMF (15mL) was stirred at 120 ℃ for 12h, cooled to room temperature, and then the mixture was poured into methanol (200mL) and stirred for 2h to isolate the crude product. The crude product was washed three times with methanol and then dried to give the pure target compound NHIQ.

Example 3:

the molecular formula isCompound A of (2.0g, 9.3mmol), methyl 4-piperidinecarboxylate (18mmol) and CH₃CN (15mL) mixture was stirred at 90 ℃ for 5h, cooled to room temperature, and the reaction mixture was concentrated by filtration under reduced pressure. Purification by column chromatography on silica gel gave compound B.

A mixture of Compound B (2.5g, 7.5mmol), hydrazine hydrate (15mL) and ethyl acetate (15mL) was stirred at 80 ℃ for 8h, after cooling to room temperature, the mixture was poured into methanol (100mL) to precipitate the crude product. The crude product was washed 5 times with methanol and then dried to give pure title compound C.

Compound C (1.5g, 6.5mmol) of formulaThe mixture of aromatic aldehyde (12mmol) and DMF (15mL) was stirred at 120 ℃ for 12h, cooled to room temperature, and then the mixture was poured into methanol (200mL) and stirred for 2h to isolate the crude product. The crude product was washed three times with methanol and then dried to give pure target compound AHIQ.

Example 4:

the molecular formula isCompound A of (2.0g, 9.3mmol), methyl 4-piperidinecarboxylate (18mmol) and CH₃CN (15mL) mixture was stirred at 90 ℃ for 5h, cooled to room temperature, and the reaction mixture was concentrated by filtration under reduced pressure. Purification by column chromatography on silica gel gave compound B.

A mixture of Compound B (2.5g, 7.5mmol), hydrazine hydrate (15mL) and ethyl acetate (15mL) was stirred at 80 ℃ for 8h, after cooling to room temperature, the mixture was poured into methanol (100mL) to precipitate the crude product. The crude product was washed 5 times with methanol and then dried to give pure title compound C.

Compound C (1.5g, 6.5mmol) of formulaThe mixture of aromatic aldehyde (12mmol) and DMF (15mL) was stirred at 120 ℃ for 12h, cooled to room temperature, and then the mixture was poured into methanol (200mL) and stirred for 2h to isolate the crude product. The crude product was washed three times with methanol and then dried to give the pure target compound TPHIQ.

The products obtained in examples 1 to 4 were subjected to nuclear magnetic testing, and it can be seen that the expected products were obtained with reference to fig. 20 to 27.

In the present invention, four target compounds were tested for photophysical properties, and the resulting product was formulated as CHCl in solution₃At a concentration of 1X 10^-5The liquid UV luminescence test and the fluorescence test were performed on mol/L solutions, and referring to FIG. 5, BHIQ, NHIQ and AHIQ have similar absorption peaks mainly in the range of 312-417nm, while TPHIQ has the largest optical bandgap energy mainly at 414nm, which can be measured byTPHIQ has the best delocalized pi-conjugation, which can be due to the presence of triphenylamine units.

Referring to FIG. 6, BHIQ, NHIQ and TPHIQ have emission wavelengths in the range of 470-499nm, while AHIQ has a stronger emission peak at 392nm from the sterically more sterically hindered anthracene and a relatively weaker emission peak at 513nm from delocalized π conjugation.

Two different single crystals BHIQ-g and BHIQ-ms of BHIQ are obtained by a solvent slow volatilization method, the BHIQ-g molecule adopts an enol form, and the BHIQ-ms molecule exists in a ketone form.

Two crystals of NHIQ, NHIQ-g and NHIQ-sb, were also obtained by slow solvent evaporation. Unlike BHIQ, both NHIQ-g and NHIQ-sb exist as ketone types.

AHIQ also exhibits polymorphism, but unlike NHIQ, both red-emitting AHIQ-r and orange-emitting AHIQ-o exist in enol form.

Referring to FIGS. 7 and 8, BHIQ-ms (λ)_em485nm) samples were lightly ground and converted to blue-green samples (λ)_em＝480nm，Φ_F21%), strong milling converted to a green sample, indicating that the multiphase body exhibited different solid state fluorescent color changes at different pressures. According to the measurement result of X-ray powder diffraction (XRD), although some diffraction peaks of the mild grinding sample show a certain degree of change, the obvious crystal form structural characteristics are still kept with BHIQ-ms, and the MFC activity caused by micro-grinding is derived from the transformation from one crystal state to another crystal state. The strong grinding treatment completely disappears the diffraction peak, and the crystalline state is converted into the amorphous state. Unlike BHIQ-ms, the fluorescence color and wavelength of BHIQ-g was observed to indicate its non-MFC properties, although grinding resulted in a crystalline to amorphous transition. The greenish ground samples obtained from BHIQ-g and BHIQ-ms could not be restored to the original crystal structure after fumigation with acetone vapor, but were converted to greenish samples.

In FIG. 7, "Gentley ground" corresponds to light grinding, "Strongy ground" corresponds to strong grinding, and "Fumed" corresponds to acetone vapor fumigation treatment. In FIG. 8, "ground" corresponds to grinding and "heated" corresponds to the acetone vapor fumigation treatment.

Referring to FIG. 9, interestingly, BHIQ-g changes in nature after three days and finally after one week to BHIQ-ms, as evidenced by fluorescence spectroscopy and XRD profiles.

Referring to fig. 10 and 13, NHIQ-g and NHIQ-sb were both converted to green samples by grinding, the morphology of which changed from crystalline to amorphous.

Referring to fig. 11, except that the fluorescence color of NHIQ-sb changed from blue-sea to green, 481nm to 515nm, and red-shifted by 34 nm. In FIG. 11, "ground" corresponds to grinding and "heated" corresponds to steaming with ethyl acetate vapor.

Referring to FIG. 12, the fluorescence spectrum and color of NHIQ-g did not change significantly. In FIG. 12, "ground" corresponds to grinding and "heated" corresponds to ethanol vapor fumigation.

Referring to fig. 10 and 13, in addition, the fluorescence spectra and x-ray diffraction (XRD) curves of the milled NHIQ-g and NHIQ-sb after fumigation with ethanol and ethyl acetate vapor show that the fluorescence spectra of both NHIQ-g and NHIQ-sb can be restored to the corresponding crystal structures by fumigation with ethanol and ethyl acetate vapor. In fig. 10, "ground" corresponds to grinding and "heated" corresponds to steaming with ethyl acetate vapor. In FIG. 13, "ground" corresponds to grinding and "heated" corresponds to ethanol vapor fumigation.

Referring to FIGS. 14 to 17, AHIQ-r and AHIQ-o both exhibited significant morphological changes from crystalline to amorphous after milling, and red emission samples (λ) were obtained_em＝624nm，Φ_F8%) and yellow emission samples. The results show that AHIQ-r has no MFC properties, whereas AHIQ-o has significant MFC characteristics. The AHIQ-o returned to the original state after the milled sample was fumigated with Dichloromethane (DCM) vapor, indicating reversibility of MFC activity. In FIG. 14, "ground" corresponds to grinding and "heated" corresponds to the treatment with steam of dichloromethane. In fig. 15, "ground" corresponds to grinding. "ground" in fig. 16 corresponds to grinding. "ground" in FIG. 17 corresponds to grinding

For TPHIQ, even though the intense and sharp diffraction peak completely disappeared, there was no significant change in fluorescence spectrum and color before and after grinding, indicating no MFC activity. Due to the existence of N-H units in the chemical structure, the possible solid acid-induced discoloration characteristics of the target compound are further researched.

BHIQ-g and BHIQ-ms were treated with trifluoroacetic acid (TFA) steam for 2min to obtain blue samples (. lamda.)_em＝437、455nm，Φ_F18%) showed significant solid acid discoloration. Acid-fumigated samples were transformed into green samples after being fumigated with Triethylamine (TEA) steam for 5min, and the change of the fluorescence color thereof was attributed to the change of the ICT effect induced by acid considering that BHIQ-g and BHIQ-ms have different chemical structures and stacking arrangement modes.

Similarly, NHIQ-sb and NHIQ-g were converted to green samples after steaming with trifluoroacetic acid (TFA) vapor for 2min, and AHIQ-sb and NHIQ-g were converted to yellow emission samples.

Referring to FIGS. 18 and 19, TPHIQ sample was first fumigated with trifluoroacetic acid (TFA) for 3min, and the fluorescence color thereof was changed from green (. lamda.) (color:)_em519nm) to orange (λ)_em＝542，620nm，Φ_FFumigate for 2min, then return to the original sample, in an alkaline vapor, showing reversible acid-discoloration activity. Indicating that the compound can be developed into a rewritable optical recording medium. In fig. 16 and 17, "+ TFA" corresponds to 3min of fumigation with trifluoroacetic acid (TFA) and "+ TFA" corresponds to 2min of continued fumigation with trifluoroacetic acid (TFA).

The invention designs and synthesizes 1-amino isoquinoline derivative to react with hydrazine hydrate to obtain 1-hydrazino isoquinoline ketone derivative, and amino is adjacent to carbonyl, so that a ketone structure and two enol structures exist besides keto-enol tautomerism. The present invention adjusts the photophysical properties of target compounds by changing the aryl groups, and these compounds exhibit solid state fluorescence with wavelengths that cover the entire visible spectrum from blue to red, with a full wavelength tunable emission spectrum.

The above description is only a preferred embodiment of the present invention, and the protection scope of the present invention is not limited to the above embodiments, and all technical solutions belonging to the idea of the present invention belong to the protection scope of the present invention. It should be noted that modifications and embellishments within the scope of the invention may occur to those skilled in the art without departing from the principle of the invention, and are considered to be within the scope of the invention.