CN113603643B - Isoquinolinone-aroylhydrazide derivative and preparation method thereof - Google Patents

Isoquinolinone-aroylhydrazide derivative and preparation method thereof Download PDF

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CN113603643B
CN113603643B CN202110905069.9A CN202110905069A CN113603643B CN 113603643 B CN113603643 B CN 113603643B CN 202110905069 A CN202110905069 A CN 202110905069A CN 113603643 B CN113603643 B CN 113603643B
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aroylhydrazide
isoquinolinone
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CN113603643A (en
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黄小波
王丹
雷云祥
刘妙昌
吴华悦
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Wenzhou University
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    • C07D217/00—Heterocyclic compounds containing isoquinoline or hydrogenated isoquinoline ring systems
    • C07D217/22—Heterocyclic compounds containing isoquinoline or hydrogenated isoquinoline ring systems with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to carbon atoms of the nitrogen-containing ring
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Abstract

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.

Description

Isoquinolinone-aroylhydrazide derivative and preparation method thereof
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 realize the purpose, the invention provides the following technical scheme:
an isoquinolone-aroylhydrazide derivative,
the molecular formula is as follows:
Figure GDA0004015830320000021
wherein Ar is
Figure GDA0004015830320000022
/>
Figure GDA0004015830320000023
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:
Figure GDA0004015830320000024
as a further improvement of the present invention,
the aromatic aldehyde is:
Figure GDA0004015830320000031
as a further improvement of the present invention,
the method comprises the following steps:
the molecular formula is
Figure GDA0004015830320000032
Mixing 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 isoquinolinone-aroylhydrazide derivative.
As a further improvement of the present invention,
the solvent A is CH 3 CN。
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, the mixture is cooled to room temperature, the reaction mixture is filtered and concentrated under reduced pressure, and the mixture is purified by column chromatography on silica gel to obtain a 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 the 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-aroylhydrazide derivative.
The reaction equation of the isoquinolone-aroylhydrazide derivative prepared by the invention is as follows:
Figure GDA0004015830320000051
the invention designs and synthesizes 1-amino isoquinoline derivative to react with hydrazine hydrate to obtain 1-hydrazino isoquinolone-aroylhydrazide derivative, and the amino is adjacent to carbonyl, so that besides keto-enol tautomerism, a keto-type structure and two enol-type structures also exist. 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 showing the structure conversion of NHIQ compound 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 the compound liquids 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 XRD curves of BHIQ-ms morphology of 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 profiles under different conditions of NHIQ-sb morphology of compound NHIQ obtained in example 2 of the present invention;
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 profile of AHIQ-o morphology of 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 invention 1 H NMR (DMSO- d 6, 500 MHz) spectrum;
FIG. 21 shows BHIQ as a compound in example 1 of the present invention 13 C NMR(DMSO-d 6 500 MHz) spectrum;
FIG. 22 shows a reaction scheme for preparing a compound NHIQ according to example 2 of the present invention 1 H NMR (DMSO- d 6, 500 MHz) spectrum;
FIG. 23 shows the reaction scheme of compound NHIQ in example 2 of the present invention 13 C NMR(DMSO-d 6 500 MHz) spectrum; .
FIG. 24 shows AHIQ as a compound in example 3 of the present invention 1 H NMR (DMSO- d 6, 500 MHz) spectrum;
FIG. 25 shows AHIQ as a compound in example 3 of the present invention 13 C NMR(DMSO-d 6 500 MHz) spectrum;
FIG. 26 is a drawing showing TPHIQ, a compound in example 4 of the present invention 1 H NMR (DMSO- d 6, 500 MHz) spectrum;
FIG. 27 is a drawing showing TPHIQ, a compound in example 4 of the present invention 13 C NMR(DMSO-d 6 500 MHz) 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 is
Figure GDA0004015830320000071
Compound A (2.0 g,9.3 mmol), methyl 4-piperidinecarboxylate (18 mmol) and CH 3 CN (15 mL) 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 (15 mL) and ethyl acetate (15 mL) was stirred at 80 ℃ for 8h, cooled to room temperature, and the mixture was poured into methanol (100 mL) to precipitate the crude product. The crude product was washed 5 times with methanol and then dried to give pure title compound C.
The compound C (1.5g, 6.5mmol) having the molecular formula
Figure GDA0004015830320000081
The mixture of aromatic aldehyde (12 mmol) and DMF (15 mL) was stirred at 120 ℃ for 12h, cooled to room temperature, and then the mixture was poured into methanol (200 mL) and stirred for 2h to isolate the crude product. The crude product was washed three times with methanol and then dried to obtain pure target compound BHIQ.
Example 2:
the molecular formula is
Figure GDA0004015830320000082
Compound A (2.0g, 9.3mmol), methyl 4-piperidinecarboxylate (18 mmol) and CH 3 CN (15 mL) 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 (15 mL) and ethyl acetate (15 mL) was stirred at 80 ℃ for 8h, after cooling to room temperature, the mixture was poured into methanol (100 mL) 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), molecular formula
Figure GDA0004015830320000083
The mixture of aromatic aldehyde (12 mmol) and DMF (15 mL) was stirred at 120 ℃ for 12h, cooled to room temperature, and the mixture was poured into aIn alcohol (200 mL), the mixture was stirred for 2 hours, and the crude product was isolated. The crude product was washed three times with methanol and then dried to give the pure target compound NHIQ.
Example 3:
the molecular formula is
Figure GDA0004015830320000091
Compound A (2.0g, 9.3mmol), methyl 4-piperidinecarboxylate (18 mmol) and CH 3 CN (15 mL) 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 (15 mL) and ethyl acetate (15 mL) was stirred at 80 ℃ for 8h, cooled to room temperature, and the mixture was poured into methanol (100 mL) 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), molecular formula
Figure GDA0004015830320000092
The mixture of aromatic aldehyde (12 mmol) and DMF (15 mL) was stirred at 120 ℃ for 12h, cooled to room temperature, and then the mixture was poured into methanol (200 mL) 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 is
Figure GDA0004015830320000093
Compound A (2.0 g,9.3 mmol), methyl 4-piperidinecarboxylate (18 mmol) and CH 3 CN (15 mL) 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 (15 mL) and ethyl acetate (15 mL) was stirred at 80 ℃ for 8h, cooled to room temperature, and the mixture was poured into methanol (100 mL) 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), molecular formula
Figure GDA0004015830320000101
After being stirred at 120 ℃ for 12h, the mixture of aromatic aldehyde (12 mmol) and DMF (15 mL) was cooled to room temperature and poured into methanol (200 mL) and stirred for 2h, the crude product was isolated. The crude product was washed three times with methanol and then dried to give 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 solution 3 At a concentration of 1X 10 -5 The solution at mol/L, liquid uv luminescence and fluorescence tests were performed, and referring to fig. 5, bhiq, NHIQ and AHIQ had similar absorption peaks, mainly in the range of 312-417nm, while TPHIQ had the largest optical bandgap energy, mainly at 414nm, probably due to the presence of triphenylamine units, with the TPHIQ having the best delocalized pi-conjugation.
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 pi 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) em =485 nm) sample is converted into blue after slight grindingGreen sample (lambda) em ＝480nm，Φ F = 21%) and conversion to green samples after intense milling indicates that the multiphase body exhibits different solid state fluorescence 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 bluish ground samples obtained from BHIQ-g and BHIQ-ms were not restored to the original crystal structure by fumigation with acetone vapor, but were converted to bluish 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 "fused" corresponds to acetone vapor fumigation.
Referring to FIG. 9, interestingly, in the natural environment, BHIQ-g changes after three days and finally after one week to BHIQ-ms, which can be demonstrated by fluorescence spectroscopy and XRD profile.
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 34nm. In FIG. 11, "ground" corresponds to grinding and "fused" 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 "fused" 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 showed significant morphological changes from crystalline to amorphous after milling, and red emission samples (λ) were obtained em ＝624nm，Φ F = 8%) 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 "fused" corresponds to fumigation with methylene chloride vapor. 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 F = 18%) showing a pronounced solid acid discoloration behaviour. The acid-fumigated sample is converted into a green sample after being fumigated for 5min by Triethylamine (TEA) steam, and the change of the fluorescence color of the acid-fumigated sample is attributed to the change of 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, the TPHIQ sample was first fumigated with trifluoroacetic acid (TFA) for 3min, and the fluorescence color thereof was changed from green (. Lamda.) (color:. Lamda.) em =519 nm) to orange(λ em ＝542620nm，Φ F = 7%), fumigation is continued for 2min and then back to the original sample, showing reversible acid-colour change activity in alkaline vapour. Indicating that the compound can be developed into a rewritable optical recording medium. In fig. 16 and 17, "+ TFA" corresponds to 3min of trifluoroacetic acid (TFA) fumigation and "+ TFA" corresponds to 2min of trifluoroacetic acid (TFA) fumigation.
The invention designs and synthesizes 1-amino isoquinoline derivative to react with hydrazine hydrate to obtain 1-hydrazino isoquinolone-aroylhydrazide derivative, and the amino is adjacent to carbonyl, so that besides keto-enol tautomerism, a keto-type structure and two enol-type structures also exist. 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.

Claims (10)

1. An isoquinolinone-aroylhydrazide derivative characterized by:
the molecular formula is as follows:
Figure FDA0004015830310000011
wherein Ar is
Figure FDA0004015830310000012
Figure FDA0004015830310000013
2. The isoquinolinone-aroylhydrazide derivative of claim 1, wherein:
the compound A is reacted with 4-methyl piperidine formate, hydrazine hydrate and aromatic aldehyde to obtain the compound A;
the molecular formula of the compound A is as follows:
Figure FDA0004015830310000021
3. an isoquinolinone-aroylhydrazide derivative according to claim 2, wherein:
the aromatic aldehyde is:
Figure FDA0004015830310000022
4. a process for the preparation of isoquinolinone-aroylhydrazide derivatives as claimed in any one of claims 1 to 3, characterized in that:
the method comprises the following steps:
the molecular formula is
Figure FDA0004015830310000031
Mixing 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 isoquinolinone-aroylhydrazide derivative.
5. The method for producing an isoquinolinone-aroylhydrazide derivative according to claim 4, wherein: the solvent A is CH 3 CN。
6. The method for producing an isoquinolinone-aroylhydrazide derivative according to claim 4, wherein: the solvent B is ethyl acetate.
7. The method for producing an isoquinolinone-aroylhydrazide derivative according to 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, 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.
9. The method for preparing 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 ℃, after the mixture is cooled to room temperature, the mixture is poured into methanol to precipitate a crude product, the crude product is washed for 5 times by the methanol, and then the pure target compound C is obtained after drying.
10. The method for preparing 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 isoquinolinone-aroylhydrazide derivative.
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