CN107382982B - dicyanomethylene-4H-pyran derivative and preparation method and application thereof - Google Patents

dicyanomethylene-4H-pyran derivative and preparation method and application thereof Download PDF

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CN107382982B
CN107382982B CN201710627538.9A CN201710627538A CN107382982B CN 107382982 B CN107382982 B CN 107382982B CN 201710627538 A CN201710627538 A CN 201710627538A CN 107382982 B CN107382982 B CN 107382982B
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dicyanomethylene
indole
pyran
pyran derivative
aldehyde
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CN107382982A (en
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黄小波
钱乐彬
吴华悦
周一斌
刘妙昌
高文霞
丁金昌
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Wenzhou University
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Abstract

The invention particularly relates to a dicyanomethylene-4H-pyran derivative, a preparation method and application thereof. The preparation method of the dicyanomethylene-4H-pyran derivative comprises the following steps of (1) taking 2, 6-dimethyl-4-pyrone 1 as a starting material to perform addition-elimination reaction with malononitrile to obtain an intermediate 2; (2) and carrying out addition-elimination reaction on the intermediate 2 and indole aldehyde with different alkyl chains to obtain the dicyanomethylene-4H-pyran derivative. The invention introduces indole structural units with different alkyls and dicyanomethylene-4H-pyran structural units into the field of organic solid luminescent materials, develops a plurality of novel piezoluminescence color-changing materials, and has important application in the photoelectric field. The method provided by the invention has the advantages of simple synthesis process and easy purification, and the synthesized piezoluminescent material is very suitable for preparing pressure sensors, anti-counterfeiting trademarks and other fields, and has good scientific research value and industrial application potential.

Description

dicyanomethylene-4H-pyran derivative and preparation method and application thereof
Technical Field
The invention belongs to the field of organic synthesis and application, and particularly relates to a dicyanomethylene-4H-pyran derivative, and a preparation method and application thereof.
Background
Piezoluminescence discoloration of organic molecules is a class of "smart" materials. The solid state fluorescence color can show obvious change when being stimulated by external force. And has received attention from the scientific and industrial circles due to its potential applications in the fields of fluorescent sensors, data storage, security inks, and optoelectronic devices. (see J.Am.chem.Soc.,2005,127, 11661-11665; adv.Funct.Mater.,2007,17, 3799-3807; chem.Commun.,2013,49, 273-275).
The dicyanomethylene-4H-pyran unit has a structure with an ultra-fast intramolecular fast charge transfer effect, so that the dicyanomethylene-4H-pyran unit has a longer emission wavelength and a high fluorescence quantum yield and is an excellent fluorophore for constructing a red light material, but the derivative of the dicyanomethylene-4H-pyran unit is easy to cause a phenomenon of fluorescence quenching due to a pi-pi stacking effect in an aggregation state so far, so that the application of the dicyanomethylene-4H-pyran unit as a fluorescent material in a film forming or solid state form is limited (see a document: chem. Commun.,2012,48, 6073-.
Generally, the introduction of alkyl chains into the conjugated skeleton of organic fluorescent molecules is mainly to adjust the solubility of organic molecules in organic solvents in the future, but recently some studies have shown that the introduction of different alkyl chains may also affect the luminescence properties of organic molecules in the aggregated state (see the literature: J. Mater. chem. C,2016,4, 1568-1578). In order to expand the application of dicyanomethylene-4H-pyran fluorophore in solid fluorescent materials and search and synthesize new structural molecules thereof, the invention synthesizes dicyanomethylene-4H-pyran derivatives which have good luminescence property in solid state and have piezochromic property by introducing indole units with long alkyl chains into the structural units and changing the connecting positions of the indole units and parent units.
Disclosure of Invention
The purpose of the invention is as follows: the present invention has been made keeping in mind the above problems occurring in the prior art, and a first object of the present invention is to provide dicyanomethylene-4H-pyran derivatives containing an indole unit. The second purpose of the invention is to disclose a preparation method of dicyanomethylene-4H-pyran derivative. The third purpose of the invention is to disclose the application of dicyanomethylene-4H-pyran derivative.
The applicant intends to show that the solution of the invention is carried out with the help of the national science foundation (No.21572165), here denoted thanks.
The technical scheme is as follows: dicyanomethylene-4H-pyran derivatives having the formula:
Figure BDA0001363117680000021
a process for the preparation of dicyanomethylene-4H-pyran derivatives comprising the steps of:
(1) taking 2, 6-dimethyl-4-pyrone 1 as a starting material, and carrying out addition-elimination reaction with malononitrile to obtain an intermediate 2;
(2) the intermediate 2 and indole aldehyde with different alkyl chains have addition-elimination reaction to obtain dicyanomethylene-4H-pyran derivative,
the reaction formula is shown as follows:
Figure BDA0001363117680000031
further, the step (1) comprises the following steps:
(11) adding 2, 6-dimethyl-4-pyrone 1 and malononitrile into anhydrous acetic anhydride to form a reaction solution, wherein:
the molar ratio of the 2, 6-dimethyl-4-pyrone 1 to the malononitrile to the acetic anhydride is 1 (3-40) to 3-40;
(12) stirring the reaction solution at 120-160 ℃ for reaction for 1.5-10 h;
(13) after the reaction is finished, cooling the reaction liquid to room temperature, adding excessive boiling water into the reaction liquid, separating out solids, performing suction filtration, and collecting a crude product;
(14) and (3) purifying the crude product by silica gel column chromatography with petroleum ether/ethyl acetate as an eluent in a volume ratio of (5-50): 1 to obtain an intermediate 2.
Further, the step (2) comprises the following steps:
(21) mixing piperidine and acetonitrile according to a volume ratio of 1 (20-100) to form an excessive mixed solvent;
(22) adding the intermediate 2 and indole aldehydes with different alkyl chains into the mixed solution to form a reaction solution, wherein:
the molar ratio of the intermediate 2 to the indole aldehydes with different alkyl chains is 1: (2-8);
(23) and heating the reaction solution to react for 12-48 hours at 50-100 ℃ under the protection of nitrogen, and then cooling to room temperature to obtain the dicyanomethylene-4H-pyran derivative.
Furthermore, the indole aldehydes with different alkyl chains in step (22) are indole aldehydes 3a or indole aldehydes 3b or indole aldehydes 3c or indole aldehydes 3d, and the structural formula is as follows:
Figure BDA0001363117680000041
still further, the preparation of indole aldehydes 3b, indole aldehydes 3c, indole aldehydes 3d comprises the following steps:
(221) slowly adding 10-30 molar parts of n-butyl bromide, 10-30 molar parts of iso-butane bromide or 10-30 molar parts of dodecane bromide into 400-500 molar parts of DMSO, and then adding 15-20 molar parts of indole aldehyde 3a and 15-50 molar parts of KOH into the DMSO to form a mixed solution;
(222) stirring the mixed solution at room temperature for 9-15 h, then adding 5000-6000 mol parts of water, and extracting with dichloromethane;
(223) the combined dichloromethane organic layers were washed successively with water and brine, and then with anhydrous Na2SO4Drying, distilling dichloromethane under reduced pressure to dryness to obtain a residue, purifying the residue by silica gel column chromatography and using petroleum ether/ethyl acetate with a volume ratio of (2-20): 1 to obtain indole aldehyde 3b or indole aldehyde 3c or indole aldehyde 3d, wherein the chemical formula is as follows:
Figure BDA0001363117680000042
wherein:
Figure BDA0001363117680000043
furthermore, the indole aldehydes with different alkyl chains in the step (22) are indole aldehydes 4a or indole aldehydes 4b or indole aldehydes 4c or indole aldehydes 4d, and the structural formula is as follows:
Figure BDA0001363117680000051
still further, the preparation of indole aldehydes 4b, 4c, 4d comprises the following steps:
(22a) slowly adding 10-30 molar parts of n-butyl bromide, 10-30 molar parts of iso-butane bromide or 10-30 molar parts of dodecane bromide into 400-500 molar parts of DMSO, and then adding 15-20 molar parts of indole aldehyde 4a and 15-50 molar parts of KOH into the DMSO to form a mixed solution;
(22b) stirring the mixed solution at room temperature for 9-15 h, then adding 5000-6000 mol parts of water, and extracting with dichloromethane;
(22c) the combined dichloromethane organic layers were washed successively with water and brine, and then with anhydrous Na2SO4Drying, distilling dichloromethane under reduced pressure to dryness to obtain a residue, purifying the residue by silica gel column chromatography and using petroleum ether/ethyl acetate with a volume ratio of (2-20): 1 to obtain indole aldehyde 4b or indole aldehyde 4c or indole aldehyde 4d, wherein the chemical formula is as follows:
Figure BDA0001363117680000052
wherein:
Figure BDA0001363117680000053
further, the indole aldehydes with different alkyl chains in step (22) are indole aldehydes 5a or 5b or 5c or 5d, and the structural formula is as follows:
Figure BDA0001363117680000054
still further, the preparation of indole aldehydes 5b, 5c, 5d comprises the steps of:
s221, slowly adding 10-30 molar parts of n-butyl bromide, 10-30 molar parts of iso-butane bromide or 10-30 molar parts of n-dodecane bromide into 400-500 molar parts of DMSO, and then adding 15-20 molar parts of indole aldehyde 5a and 15-50 molar parts of KOH into the DMSO to form a mixed solution;
s222, stirring the mixed solution at room temperature for 9-15 hours, then adding 5000-6000 mol parts of water, and extracting with dichloromethane;
s223 the combined dichloromethane organic layers were washed successively with water and brine, and then with anhydrous Na2SO4Drying, distilling dichloromethane under reduced pressure to dryness to obtain a residue, purifying the residue by silica gel column chromatography and using petroleum ether/ethyl acetate with a volume ratio of (2-20): 1 to obtain indole aldehyde 4b or indole aldehyde 4c or indole aldehyde 4d, wherein the chemical formula is as follows:
Figure BDA0001363117680000061
wherein
Figure BDA0001363117680000062
The dicyanomethylene-4H-pyran derivative has the characteristic of piezoluminescence discoloration property and is applied to pressure sensors and anti-counterfeiting trademarks.
The dicyanomethylene-4H-pyran derivative disclosed by the invention as well as the preparation method and the application thereof have the following beneficial effects:
the invention introduces indole structural units with different alkyls and dicyanomethylene-4H-pyran structural units into the field of organic solid luminescent materials, develops a plurality of novel piezoluminescence color-changing materials, and has important application in the photoelectric field.
The method provided by the invention has the advantages of simple synthesis process and easy purification, and the synthesized piezoluminescent material is very suitable for preparing pressure sensors, anti-counterfeiting trademarks and other fields, and has good scientific research value and industrial application potential.
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FIG. 1 is a graph showing solid fluorescence spectra of a raw sample and a ground sample of dicyanomethylene-4H-pyran derivative 6 a.
FIG. 2 is a graph showing solid fluorescence spectra of an original sample and a ground sample of dicyanomethylene-4H-pyran derivative 6 b.
FIG. 3 is a solid fluorescence spectrum of the original sample of dicyanomethylene-4H-pyran derivative 6c, the ground sample, and the ground sample fumigated with ethyl acetate vapor.
FIG. 4 is a solid fluorescence spectrum of the original sample of dicyanomethylene-4H-pyran derivative 6d, the ground sample, and the ground sample fumigated with ethyl acetate vapor.
FIG. 5 is a solid fluorescence spectrum of the original sample of dicyanomethylene-4H-pyran derivative 7a, the ground sample, and the ground sample fumigated with ethyl acetate vapor.
FIG. 6 is a solid fluorescence spectrum of the original sample of dicyanomethylene-4H-pyran derivative 7b, the ground sample, and the ground sample fumigated with ethyl acetate vapor.
FIG. 7 is a solid fluorescence spectrum of the original sample of dicyanomethylene-4H-pyran derivative 7c, the ground sample, and the ground sample fumigated with ethyl acetate vapor.
FIG. 8 is a graph showing solid fluorescence spectra of a raw sample and a ground sample of dicyanomethylene-4H-pyran derivative 7 d.
FIG. 9 is a graph of the solid fluorescence spectra of the original sample of dicyanomethylene-4H-pyran derivative 8a, the ground sample, and the ground sample after fumigation with ethyl acetate vapor.
FIG. 10 is a graph showing solid fluorescence spectra of an original sample and a ground sample of dicyanomethylene-4H-pyran derivative 8 b.
FIG. 11 is a graph showing solid fluorescence spectra of a raw sample and a ground sample of dicyanomethylene-4H-pyran derivative 8 c.
FIG. 12 is a graph showing solid fluorescence spectra of a raw sample and a ground sample of dicyanomethylene-4H-pyran derivative 8 d.
The specific implementation mode is as follows:
the following describes in detail specific embodiments of the present invention.
Detailed description of the preferred embodiment 1
dicyanomethylene-4H-pyran derivatives having the formula:
Figure BDA0001363117680000071
a process for the preparation of dicyanomethylene-4H-pyran derivatives comprising the steps of:
(1) taking 2, 6-dimethyl-4-pyrone 1 as a starting material, and carrying out addition-elimination reaction with malononitrile to obtain an intermediate 2;
(2) and carrying out addition-elimination reaction on the intermediate 2 and indole aldehyde with different alkyl chains to obtain the dicyanomethylene-4H-pyran derivative.
Characterization of dicyanomethylene-4H-pyran derivative 6 a:1H NMR(DMSO-d6,500MHz)，(ppm):11.87(s,2H),8.25(d,J＝8.0Hz,2H),8.04-7.98(m,4H),7.51(d,J＝8.0Hz,2H),7.28-7.19(m,6H),6.92(s,2H)。13C NMR(DMSO-d6,125MHz)，(ppm):160.3,156.3,137.6,132.6,132.5,124.6,122.7,120.9,120.8,116.6,113.3,112.7,112.4,104.3,52.6。MS(ESI,m/z):427.10(M++H)。Anal.calcd for C28H18N4O:C,78.86；H,4.25；N,13.14.Found:C,79.29；H,4.22；N,13.22。
further, the step (1) comprises the following steps:
(11) adding 2, 6-dimethyl-4-pyrone 1 and malononitrile into anhydrous acetic anhydride to form a reaction solution, wherein:
the molar ratio of the 2, 6-dimethyl-4-pyrone 1 to the malononitrile to the acetic anhydride is 1:3: 3;
(12) stirring the reaction solution at 120 ℃ to react for 10 h;
(13) after the reaction is finished, cooling the reaction liquid to room temperature, adding excessive boiling water into the reaction liquid, separating out solids, performing suction filtration, and collecting a crude product;
(14) the crude product was purified by silica gel column chromatography using petroleum ether/ethyl acetate as eluent in a volume ratio of (5: 1) to give intermediate 2.
Further, the step (2) comprises the following steps:
(21) mixing piperidine and acetonitrile according to the volume ratio of 1:20 to form an excessive mixed solvent;
(22) adding the intermediate 2 and indole aldehydes with different alkyl chains into the mixed solution to form a reaction solution, wherein:
the molar ratio of the intermediate 2 to the indole aldehydes with different alkyl chains is 1: 2;
(23) and heating the reaction solution at 50 ℃ for 48 hours under the protection of nitrogen, and then cooling to room temperature to obtain the dicyanomethylene-4H-pyran derivative.
Further, the indole aldehydes with different alkyl chains in step (22) are indole aldehydes 3a, and the structural formula is as follows:
Figure BDA0001363117680000081
the dicyanomethylene-4H-pyran derivative has the characteristic of piezoluminescence discoloration property and is applied to pressure sensors and anti-counterfeiting trademarks.
FIG. 1 is a graph showing solid fluorescence spectra of a raw sample and a ground sample of dicyanomethylene-4H-pyran derivative 6 a. The emission wavelength of the original sample was 634nm and the emission wavelength of the milled sample was 655nm, red-shifted by 21 nm. The original sample, which emits red fluorescence, is ground to emit red fluorescence. The dicyanomethylene-4H-pyran derivative 6a has no piezochromic property because there is no significant change in fluorescence before and after grinding.
Specific example 2
dicyanomethylene-4H-pyran derivatives having the formula:
Figure BDA0001363117680000091
a process for the preparation of dicyanomethylene-4H-pyran derivatives comprising the steps of:
(1) taking 2, 6-dimethyl-4-pyrone 1 as a starting material, and carrying out addition-elimination reaction with malononitrile to obtain an intermediate 2;
(2) and carrying out addition-elimination reaction on the intermediate 2 and indole aldehyde with different alkyl chains to obtain the dicyanomethylene-4H-pyran derivative.
Characterization of dicyanomethylene-4H-pyran derivative 6 b:1H NMR(CDCl3,500MHz)，(ppm):7.94(d,J＝7.5Hz,2H),7.72(d,J＝15.5Hz,2H),7.51(s,2H),7.23(d,J＝8.0Hz,2H),7.36-7.30(m,4H),6.67(d,J＝16.0Hz,2H),6.48(s,2H),4.19(t,J＝7.0Hz,4H),1.91-1.87(m,4H),1.43-1.37(m,4H),0.99(t,J＝7.0Hz,6H)。13C NMR(CDCl3,125MHz)，(ppm):159.7,156.2,137.6,132.1,131.2,125.9,123.2,121.6,120.5,116.5,113.5,112.9,110.5,104.8,55.6,46.7,32.0,20.2,13.6。MS(ESI,m/z):539.25(M++H)。Anal.calcd for C36H34N4O:C,80.27；H,6.36；N,10.40.Found:C,80.81；H,6.41；N,10.49。
further, the step (1) comprises the following steps:
(11) adding 2, 6-dimethyl-4-pyrone 1 and malononitrile into anhydrous acetic anhydride to form a reaction solution, wherein:
the molar ratio of the 2, 6-dimethyl-4-pyrone 1 to the malononitrile to the acetic anhydride is 1:40: 40;
(12) stirring the reaction solution at 160 ℃ to react for 1.5 h;
(13) after the reaction is finished, cooling the reaction liquid to room temperature, adding excessive boiling water into the reaction liquid, separating out solids, performing suction filtration, and collecting a crude product;
(14) and (3) purifying the crude product by silica gel column chromatography with petroleum ether/ethyl acetate as an eluent in a volume ratio of 50:1 to obtain an intermediate 2.
Further, the step (2) comprises the following steps:
(21) mixing piperidine and acetonitrile according to the volume ratio of 1:100 to form an excessive mixed solvent;
(22) adding the intermediate 2 and indole aldehydes with different alkyl chains into the mixed solution to form a reaction solution, wherein:
the molar ratio of the intermediate 2 to the indole aldehydes with different alkyl chains is 1: 8;
(23) and heating the reaction solution at 100 ℃ for 12 hours under the protection of nitrogen, and then cooling to room temperature to obtain the dicyanomethylene-4H-pyran derivative.
Further, the indole aldehydes with different alkyl chains in step (22) are indole aldehydes 3b, which have the following structural formula:
Figure BDA0001363117680000101
still further, the preparation of indole aldehyde 3b comprises the steps of:
(221) slowly adding 30 molar parts of n-butyl bromide into 500 molar parts of DMSO, and then adding 20 molar parts of indole aldehyde 3a and 50 molar parts of KOH into the DMSO to form a mixed solution;
(222) stirring the mixed solution at room temperature for 15 hours, then adding 5000 mol parts of water, and extracting with dichloromethane;
(223) the combined dichloromethane organic layers were washed successively with water and brine, and then with anhydrous Na2SO4Drying, distillation of dichloromethane to dryness under reduced pressure gives a residue which is purified by column chromatography on silica gel using petroleum ether/ethyl acetate in a volume ratio of 20:1 to give indole aldehyde 3 b.
Characterization of 3 b:1H NMR(CDCl3,500MHz)，(ppm):9.95(s,1H),8.31(dd,3J＝6.5Hz,4J＝2.5Hz,1H),7.65(s,1H),7.36-7.27(m,3H),4.09(t,J＝7.5Hz,2H),1.84-1.79(m,2H),1.35-1.31(m,2H),0.93(t,J＝7.5Hz,3H)。13C NMR(CDCl3,125MHz)，(ppm):184.2,138.2,137.1,125.2,123.6,122.6,121.8,117.8,110.0,46.7,31.5,19.8,13.4。
the dicyanomethylene-4H-pyran derivative has the characteristic of piezoluminescence discoloration property and is applied to pressure sensors and anti-counterfeiting trademarks.
FIG. 2 is a graph showing solid fluorescence spectra of an original sample and a ground sample of dicyanomethylene-4H-pyran derivative 6 b. The emission wavelength of the original sample was 622nm, the emission wavelength of the milled sample was 631nm, which was red-shifted by 9 nm. The original sample, which emits red fluorescence, is ground to emit red fluorescence. The dicyanomethylene-4H-pyran derivative 6b has no piezochromic property because there is no significant change in fluorescence before and after grinding.
Specific example 3
dicyanomethylene-4H-pyran derivatives having the formula:
Figure BDA0001363117680000111
a process for the preparation of dicyanomethylene-4H-pyran derivatives comprising the steps of:
(1) taking 2, 6-dimethyl-4-pyrone 1 as a starting material, and carrying out addition-elimination reaction with malononitrile to obtain an intermediate 2;
(2) and carrying out addition-elimination reaction on the intermediate 2 and indole aldehyde with different alkyl chains to obtain the dicyanomethylene-4H-pyran derivative.
Characterization of dicyanomethylene-4H-pyran derivative 6 c:1H NMR(CDCl3,500MHz)，(ppm):7.96-7.94(m,2H),7.73(dd,3J＝16.0Hz,4J＝3.5Hz,2H),7.49(d,J＝3.5Hz,2H),7.42(dd,3J＝7.5Hz,4J＝3.0Hz,2H),7.36-7.27(m,4H),6.69(dd,3J＝16.0Hz,4J＝3.5Hz,2H),6.49(d,J＝3.5Hz,2H),3.39(dd,3J＝7.0Hz,4J＝3.5Hz,4H),2.29-2.24(m,2H),0.99(dd,3J＝6.5Hz,4J＝3.5Hz,12H)。13C NMR(CDCl3,125MHz)，(ppm):159.7,156.2,137.8,132.8,131.3,125.8,123.2,121.6,120.5,116.5,113.6,112.7,110.7,104.8,55.5,54.5,29.3,20.3。MS(ESI,m/z):539.25(M++H)。Anal.calcd for C36H34N4O:C,80.27；H,6.36；N,10.40.Found:C,80.92；H,6.39；N,10.50。
further, the step (1) comprises the following steps:
(11) adding 2, 6-dimethyl-4-pyrone 1 and malononitrile into anhydrous acetic anhydride to form a reaction solution, wherein:
the molar ratio of the 2, 6-dimethyl-4-pyrone 1 to the malononitrile to the acetic anhydride is 1:10: 10;
(12) stirring the reaction solution at 140 ℃ to react for 5 h;
(13) after the reaction is finished, cooling the reaction liquid to room temperature, adding excessive boiling water into the reaction liquid, separating out solids, performing suction filtration, and collecting a crude product;
(14) and (3) purifying the crude product by silica gel column chromatography with petroleum ether/ethyl acetate as an eluent in a volume ratio of 10:1 to obtain an intermediate 2.
Further, the step (2) comprises the following steps:
(21) mixing piperidine and acetonitrile according to the volume ratio of 1:50 to form an excessive mixed solvent;
(22) adding the intermediate 2 and indole aldehydes with different alkyl chains into the mixed solution to form a reaction solution, wherein:
the molar ratio of the intermediate 2 to the indole aldehydes with different alkyl chains is 1: 5;
(23) and heating the reaction solution at 80 ℃ for 24 hours under the protection of nitrogen, and then cooling to room temperature to obtain the dicyanomethylene-4H-pyran derivative.
Further, the indole aldehydes with different alkyl chains in step (22) are indole aldehydes 3c, which have the following structural formula:
Figure BDA0001363117680000121
characterization of indole aldehyde 3 c:1H NMR(CDCl3,500MHz)，(ppm):9.96(s,1H),8.29(dd,3J＝6.5Hz,4J＝3.0Hz,1H),7.64(s,1H),7.34-7.26(m,3H),3.91(d,J＝7.5Hz,2H),2.24-2.16(m,1H),0.92(d,J＝6.5Hz,6H)。13C NMR(CDCl3,125MHz)，(ppm):184.4,138.8,137.4,125.3,123.7,122.7,121.9,117.8,110.2,54.7,29.0,20.0。
still further, the preparation of indole aldehyde 3c comprises the steps of:
(221) slowly adding 20 molar parts of bromoisobutane into 423 molar parts of DMSO, and then adding 17 molar parts of indolal 3a and 25.6 molar parts of KOH into the DMSO to form a mixed solution;
(222) stirring the mixed solution at room temperature for 12 hours, then adding 5555 mol parts of water, and extracting with dichloromethane;
(223) the combined dichloromethane organic layers were washed successively with water and brine, and then with anhydrous Na2SO4Drying, distillation of dichloromethane to dryness under reduced pressure gave a residue which was purified by silica gel column chromatography using 4:1 petroleum ether/ethyl acetate by volume to give indole aldehyde 3 c.
The dicyanomethylene-4H-pyran derivative has the characteristic of piezoluminescence discoloration property and is applied to pressure sensors and anti-counterfeiting trademarks.
FIG. 3 is a solid fluorescence spectrum of the original sample of dicyanomethylene-4H-pyran derivative 6c, the ground sample, and the ground sample fumigated with ethyl acetate vapor. The emission wavelength of the original sample is 601nm, the emission wavelength of the ground sample is 632nm, the red shift is 31nm, and the emission wavelength of the ground sample is recovered to 618nm after fumigation by ethyl acetate vapor solvent. The original sample, which emitted orange fluorescence, emitted red fluorescence after grinding, and was again recovered as orange fluorescence by steam fumigation with ethyl acetate. The dicyanomethylene-4H-pyran derivative 6c has a piezochromic property because the fluorescence color changes significantly before and after the grinding.
Specific example 4
dicyanomethylene-4H-pyran derivatives having the formula:
Figure BDA0001363117680000131
a process for the preparation of dicyanomethylene-4H-pyran derivatives comprising the steps of:
(1) taking 2, 6-dimethyl-4-pyrone 1 as a starting material, and carrying out addition-elimination reaction with malononitrile to obtain an intermediate 2;
(2) and carrying out addition-elimination reaction on the intermediate 2 and indole aldehyde with different alkyl chains to obtain the dicyanomethylene-4H-pyran derivative.
Characterization of dicyanomethylene-4H-pyran derivative 6 d:1H NMR(CDCl3,500MHz)，(ppm):7.94(d,J＝8.0Hz,2H),7.72(d,J＝15.5Hz,2H),7.50(s,2H),7.42(d,J＝8.5Hz,2H),7.36-7.29(m,4H),6.67(d,J＝16.0Hz,2H),6.47(s,2H),4.17(t,J＝7.0Hz,4H),1.92-1.89(m,4H),1.35-1.25(m,36H),0.87(t,J＝7.0Hz,6H)。13C NMR(CDCl3,125MHz)，(ppm):159.7,156.2,137.6,132.1,131.2,125.9,123.2,121.6,120.5,116.4,113.5,112.9,110.5,104.7,55.6,47.0,31.9,30.0,29.6,29.5,29.4,29.3,29.2,27.0,22.7,14.1。MS(ESI,m/z):763.45(M++H)。Anal.calcd for C52H66N4O:C,81.84；H,8.72；N,7.34.Found:C,82.34；H,8.67；N,7.40。
further, the step (1) comprises the following steps:
(11) adding 2, 6-dimethyl-4-pyrone 1 and malononitrile into anhydrous acetic anhydride to form a reaction solution, wherein:
the molar ratio of the 2, 6-dimethyl-4-pyrone 1 to the malononitrile to the acetic anhydride is 1:10: 20;
(12) stirring the reaction solution at 150 ℃ to react for 4 h;
(13) after the reaction is finished, cooling the reaction liquid to room temperature, adding excessive boiling water into the reaction liquid, separating out solids, performing suction filtration, and collecting a crude product;
(14) and (3) purifying the crude product by silica gel column chromatography with petroleum ether/ethyl acetate as an eluent in a volume ratio of 8:1 to obtain an intermediate 2.
Further, the step (2) comprises the following steps:
(21) mixing piperidine and acetonitrile according to the volume ratio of 1:30 to form an excessive mixed solvent;
(22) adding the intermediate 2 and indole aldehydes with different alkyl chains into the mixed solution to form a reaction solution, wherein:
the molar ratio of the intermediate 2 to the indole aldehydes with different alkyl chains is 1: 3;
(23) and heating the reaction solution at 70 ℃ for 16 hours under the protection of nitrogen, and then cooling to room temperature to obtain the dicyanomethylene-4H-pyran derivative.
Further, the indole aldehydes with different alkyl chains in the step (22) are indole aldehydes 3d, and the structural formula is as follows:
Figure BDA0001363117680000141
characterization of indole aldehyde 3 d:1H NMR(CDCl3,500MHz)，(ppm):10.00(s,1H),8.31(dd,3J＝6.5Hz,4J＝2.0Hz,1H),7.70(s,1H),7.38-7.29(m,3H),4.15(t,J＝7.0Hz,2H),1.90-1.87(m,2H),1.33-1.25(m,18H),0.88(t,J＝7.0Hz,3H)。13C NMR(CDCl3,125MHz)，(ppm):184.3,138.1,137.2,125.5,123.8,122.8,122.1,118.0,110.0,47.3,31.9,29.7,29.53,29.46,29.37,29.27,29.1,26.8,22.6,14.0。
still further, the preparation of indole aldehyde 3d comprises the steps of:
(221) slowly adding 10 molar parts of bromododecane into 400 molar parts of DMSO, and then adding 15 molar parts of indole aldehyde 3a and 15 molar parts of KOH into the DMSO to form a mixed solution;
(222) stirring the mixed solution at room temperature for 9 hours, then adding 5000 mol parts of water, and extracting with dichloromethane;
(223) the combined dichloromethane organic layers were washed successively with water and brine, and then with anhydrous Na2SO4Drying, distillation of dichloromethane to dryness under reduced pressure gave a residue which was purified by silica gel column chromatography using 2:1 petroleum ether/ethyl acetate by volume to afford indole aldehyde 3 d.
The dicyanomethylene-4H-pyran derivative has the characteristic of piezoluminescence discoloration property and is applied to pressure sensors and anti-counterfeiting trademarks.
FIG. 4 is a solid fluorescence spectrum of the original sample of dicyanomethylene-4H-pyran derivative 6d, the ground sample, and the ground sample fumigated with ethyl acetate vapor. The emission wavelength of the original sample is 591nm, the emission wavelength of the ground sample is changed into 604nm, the red shift is 13nm, and the emission wavelength of the ground sample is recovered to 592nm after fumigation by ethyl acetate vapor solvent. The original sample emitting yellow fluorescence emits red fluorescence after being ground, and then is restored to yellow fluorescence after being fumigated by ethyl acetate steam. The dicyanomethylene-4H-pyran derivative 6d has a piezochromic property because the fluorescence color changes significantly before and after the grinding.
Specific example 5
dicyanomethylene-4H-pyran derivatives having the formula:
Figure BDA0001363117680000151
a process for the preparation of dicyanomethylene-4H-pyran derivatives comprising the steps of:
(1) taking 2, 6-dimethyl-4-pyrone 1 as a starting material, and carrying out addition-elimination reaction with malononitrile to obtain an intermediate 2;
(2) and carrying out addition-elimination reaction on the intermediate 2 and indole aldehyde with different alkyl chains to obtain the dicyanomethylene-4H-pyran derivative.
Characterization of dicyanomethylene-4H-pyran derivative 7 a:1H NMR(DMSO-d6,500MHz)，(ppm):11.50(s,2H),8.06(d,J＝16.5Hz,2H),7.58-7.46(m,8H),7.21(d,J＝7.5Hz,2H),7.10(s,4H)。13CNMR(DMSO-d6,125MHz)，(ppm):159.3,156.3,137.4,136.5,127.1,126.4,126.0,121.6,121.1,118.6,115.9,114.0,106.9,100.6,55.7。MS(ESI,m/z):427.10(M++H)。Anal.calcdfor C28H18N4O:C,78.86；H,4.25；N,13.14.Found:C,79.25；H,4.23；N,13.02。
further, the step (1) comprises the following steps:
(11) adding 2, 6-dimethyl-4-pyrone 1 and malononitrile into anhydrous acetic anhydride to form a reaction solution, wherein:
the molar ratio of the 2, 6-dimethyl-4-pyrone 1 to the malononitrile to the acetic anhydride is 1:3: 3;
(12) stirring the reaction solution at 120 ℃ to react for 10 h;
(13) after the reaction is finished, cooling the reaction liquid to room temperature, adding excessive boiling water into the reaction liquid, separating out solids, performing suction filtration, and collecting a crude product;
(14) and (3) purifying the crude product by silica gel column chromatography with petroleum ether/ethyl acetate as an eluent in a volume ratio of 5:1 to obtain an intermediate 2.
Further, the step (2) comprises the following steps:
(21) mixing piperidine and acetonitrile according to the volume ratio of 1:20 to form an excessive mixed solvent;
(22) adding the intermediate 2 and indole aldehydes with different alkyl chains into the mixed solution to form a reaction solution, wherein:
the molar ratio of the intermediate 2 to the indole aldehydes with different alkyl chains is 1: 2;
(23) and heating the reaction solution at 50 ℃ for 12 hours under the protection of nitrogen, and then cooling to room temperature to obtain the dicyanomethylene-4H-pyran derivative.
Further, the indole aldehyde with different alkyl chains in the step (22) is indole aldehyde 4a, which has the following structural formula:
Figure BDA0001363117680000171
the dicyanomethylene-4H-pyran derivative has the characteristic of piezoluminescence discoloration property and is applied to pressure sensors and anti-counterfeiting trademarks.
FIG. 5 is a solid fluorescence spectrum of the original sample of dicyanomethylene-4H-pyran derivative 7a, the ground sample, and the ground sample fumigated with ethyl acetate vapor. The emission wavelength of the original sample is 607nm, the emission wavelength of the ground sample is changed to 634nm, the red shift is 27nm, and the emission wavelength of the ground sample is recovered to 613nm by fumigating with ethyl acetate vapor solvent. The original sample, which emitted orange fluorescence, emitted red fluorescence after grinding, and was again recovered as orange fluorescence by steam fumigation with ethyl acetate. The dicyanomethylene-4H-pyran derivative 7a has a piezochromic property because the fluorescence color changes significantly before and after the grinding.
Specific example 6
dicyanomethylene-4H-pyran derivatives having the formula:
Figure BDA0001363117680000172
a process for the preparation of dicyanomethylene-4H-pyran derivatives comprising the steps of:
(1) taking 2, 6-dimethyl-4-pyrone 1 as a starting material, and carrying out addition-elimination reaction with malononitrile to obtain an intermediate 2;
(2) and carrying out addition-elimination reaction on the intermediate 2 and indole aldehyde with different alkyl chains to obtain the dicyanomethylene-4H-pyran derivative.
Characterization of dicyanomethylene-4H-pyran derivative 7 b:1H NMR(CDCl3,500MHz)，(ppm):7.92(d,J＝16.0Hz,2H),7.42(d,J＝8.5Hz,2H),7.37(d,J＝7.0Hz,2H),7.28-7.23(m,4H),6.86(d,J＝16.0Hz,2H),6.77(d,J＝2.5Hz,2H),6.55(s,2H),4.16(t,J＝7.0Hz,4H),1.87-1.81(m,4H),1.40-1.32(m,4H),0.95(t,J＝7.0Hz,6H)。13C NMR(CDCl3,125MHz)，(ppm):158.6,156.0,136.9,136.6,129.6,127.5,126.8,121.6,119.9,118.3,115.6,111.9,106.7,99.3,58.6,46.4,32.4,20.2,13.6。MS(EI,m/z):538.29(M+,56％),495.23(8％),394.25(22％),226.10(57％),186.12(49％)。Anal.calcd for C36H34N4O:C,80.27；H,6.36；N,10.40.Found:C,80.83；H,6.33；N,10.32。
further, the step (1) comprises the following steps:
(11) adding 2, 6-dimethyl-4-pyrone 1 and malononitrile into anhydrous acetic anhydride to form a reaction solution, wherein:
the molar ratio of the 2, 6-dimethyl-4-pyrone 1 to the malononitrile to the acetic anhydride is 1:3: 3;
(12) stirring the reaction solution at 120 ℃ to react for 10 h;
(13) after the reaction is finished, cooling the reaction liquid to room temperature, adding excessive boiling water into the reaction liquid, separating out solids, performing suction filtration, and collecting a crude product;
(14) and (3) purifying the crude product by silica gel column chromatography with petroleum ether/ethyl acetate as an eluent in a volume ratio of 5:1 to obtain an intermediate 2.
Further, the step (2) comprises the following steps:
(21) mixing piperidine and acetonitrile according to the volume ratio of 1:20 to form an excessive mixed solvent;
(22) adding the intermediate 2 and indole aldehydes with different alkyl chains into the mixed solution to form a reaction solution, wherein:
the molar ratio of the intermediate 2 to the indole aldehydes with different alkyl chains is 1: 2;
(23) and heating the reaction solution at 50 ℃ for 48 hours under the protection of nitrogen, and then cooling to room temperature to obtain the dicyanomethylene-4H-pyran derivative.
Further, the indole aldehyde with different alkyl chains in the step (22) is indole aldehyde 4b, which has the following structural formula:
Figure BDA0001363117680000181
characterization of indole aldehyde 4 b:1H NMR(CDCl3,500MHz)，(ppm):10.25(s,1H),7.62(d,J＝7.5Hz,2H),7.35-7.29(m,3H),4.17(t,J＝7.0Hz,2H),1.85-1.79(m,2H),1.35-1.30(m,2H),0.94(t,J＝7.5Hz,3H)。13C NMR(CDCl3,125MHz)，(ppm):192.9,136.6,131.2,128.4,126.9,126.3,120.6,115.6,101.3,46.1,32.4,20.0,13.5。
still further, the preparation of indole aldehyde 4b comprises the steps of:
(22a) slowly adding 10 molar parts of n-butyl bromide into 400 molar parts of DMSO, and then adding 15 molar parts of indole aldehyde 4a and 15 molar parts of KOH into the DMSO to form a mixed solution;
(22b) stirring the mixed solution at room temperature for 9 hours, then adding 5000 mol parts of water, and extracting with dichloromethane;
(22c) the combined dichloromethane organic layers were washed successively with water and brine, and then with anhydrous Na2SO4Drying, distillation of dichloromethane to dryness under reduced pressure gives a residue which is purified by column chromatography on silica gel using petroleum ether/ethyl acetate in a volume ratio of 2:1 to give indole aldehyde 4 b.
The dicyanomethylene-4H-pyran derivative has the characteristic of piezoluminescence discoloration property and is applied to pressure sensors and anti-counterfeiting trademarks.
FIG. 6 is a solid fluorescence spectrum of the original sample of dicyanomethylene-4H-pyran derivative 7b, the ground sample, and the ground sample fumigated with ethyl acetate vapor. The emission wavelength of the original sample is 588nm, the emission wavelength of the ground sample is 621nm, the red shift is 33nm, and the emission wavelength of the ground sample is recovered to 583nm after fumigation by ethyl acetate steam solvent. The original sample emitting yellow fluorescence emits red fluorescence after being ground, and then is restored to yellow fluorescence after being fumigated by ethyl acetate steam. The dicyanomethylene-4H-pyran derivative 7b has a piezochromic property because the fluorescence color changes significantly before and after the grinding.
Specific example 7
dicyanomethylene-4H-pyran derivatives having the formula:
Figure BDA0001363117680000201
a process for the preparation of dicyanomethylene-4H-pyran derivatives comprising the steps of:
(1) taking 2, 6-dimethyl-4-pyrone 1 as a starting material, and carrying out addition-elimination reaction with malononitrile to obtain an intermediate 2;
(2) and carrying out addition-elimination reaction on the intermediate 2 and indole aldehyde with different alkyl chains to obtain the dicyanomethylene-4H-pyran derivative.
Characterization of dicyanomethylene-4H-pyran derivative 7 c:1H NMR(CDCl3,500MHz)，(ppm):7.99(d,J＝16.0Hz,2H),7.42(dd,3J＝14.0Hz,4J＝8.0Hz,4H),7.29-7.27(m,4H),6.93(d,J＝16.0Hz,2H),6.82(d,J＝2.5Hz,2H),6.64(s,2H),3.99(d,J＝7.5Hz,4H),2.28-2.20(m,2H),0.97(d,J＝6.5Hz,12H)。13C NMR(CDCl3,125MHz)，(ppm):158.7,156.0,137.0,136.9,130.2,127.4,126.9,121.6,120.0,118.4,115.6,112.1,106.7,99.2,58.8,54.4,29.7,20.3。MS(ESI,m/z):539.25(M++H).Anal.calcd for C36H34N4O:C,80.27；H,6.36；N,10.40.Found:C,79.86；H,6.32；N,10.35。
further, the step (1) comprises the following steps:
(11) adding 2, 6-dimethyl-4-pyrone 1 and malononitrile into anhydrous acetic anhydride to form a reaction solution, wherein:
the molar ratio of the 2, 6-dimethyl-4-pyrone 1 to the malononitrile to the acetic anhydride is 1:40: 40;
(12) stirring the reaction solution at 160 ℃ to react for 1.5 h;
(13) after the reaction is finished, cooling the reaction liquid to room temperature, adding excessive boiling water into the reaction liquid, separating out solids, performing suction filtration, and collecting a crude product;
(14) and (3) purifying the crude product by silica gel column chromatography with petroleum ether/ethyl acetate as an eluent in a volume ratio of 50:1 to obtain an intermediate 2.
Further, the step (2) comprises the following steps:
(21) mixing piperidine and acetonitrile according to the volume ratio of 1:100 to form an excessive mixed solvent;
(22) adding the intermediate 2 and indole aldehydes with different alkyl chains into the mixed solution to form a reaction solution, wherein:
the molar ratio of the intermediate 2 to the indole aldehydes with different alkyl chains is 1: 8;
(23) and heating the reaction solution at 100 ℃ for 48 hours under the protection of nitrogen, and then cooling to room temperature to obtain the dicyanomethylene-4H-pyran derivative.
Further, the indole aldehyde with different alkyl chains in the step (22) is indole aldehyde 4c, which has the following structural formula:
Figure BDA0001363117680000211
characterization of indole aldehyde 4 c:1H NMR(CDCl3,500MHz)，(ppm):10.24(s,1H),7.59(d,J＝7.5Hz,2H),7.32-7.28(m,3H),3.94(d,J＝7.5Hz,2H),2.21-2.13(m,1H),0.90(d,J＝7.0Hz,6H)。13C NMR(CDCl3,125MHz)，(ppm):193.0,137.0,131.8,128.4,126.9,126.2,120.6,115.8,101.3,54.1,29.7,20.1。
still further, the preparation of indole aldehyde 4c comprises the steps of:
(22a) slowly adding 30 molar parts of bromoisobutane into 400-500 molar parts of DMSO, and then adding 20 molar parts of indolal 4a and 50 molar parts of KOH into the DMSO to form a mixed solution;
(22b) stirring the mixed solution at room temperature for 15 hours, then adding 6000 mol parts of water, and extracting with dichloromethane;
(22c) the combined dichloromethane organic layers were washed successively with water and brine, and then with anhydrous Na2SO4Drying, distillation of dichloromethane to dryness under reduced pressure gives a residue which is purified by column chromatography on silica gel using petroleum ether/ethyl acetate in a volume ratio of 20:1 to give indole aldehyde 4 c.
The dicyanomethylene-4H-pyran derivative has the characteristic of piezoluminescence discoloration property and is applied to pressure sensors and anti-counterfeiting trademarks.
FIG. 7 is a solid fluorescence spectrum of the original sample of dicyanomethylene-4H-pyran derivative 7c, the ground sample, and the ground sample fumigated with ethyl acetate vapor. The emission wavelength of the original sample is 586nm, the emission wavelength of the ground sample becomes 626nm, the red shift is 40nm, and the emission wavelength of the ground sample is recovered to 585nm by fumigating with ethyl acetate vapor solvent. The original sample emitting yellow fluorescence emits red fluorescence after being ground, and then is restored to yellow fluorescence after being fumigated by ethyl acetate steam. The dicyanomethylene-4H-pyran derivative 7c has a piezochromic property because the fluorescence color changes significantly before and after the grinding.
Specific example 8
dicyanomethylene-4H-pyran derivatives having the formula:
Figure BDA0001363117680000221
a process for the preparation of dicyanomethylene-4H-pyran derivatives comprising the steps of:
(1) taking 2, 6-dimethyl-4-pyrone 1 as a starting material, and carrying out addition-elimination reaction with malononitrile to obtain an intermediate 2;
(2) and carrying out addition-elimination reaction on the intermediate 2 and indole aldehyde with different alkyl chains to obtain the dicyanomethylene-4H-pyran derivative.
Characterization of dicyanomethylene-4H-pyran derivative 7 d:1H NMR(CDCl3,500MHz)，(ppm):7.94(d,J＝16.0Hz,2H),7.39(dd,3J＝19.0Hz,4J＝7.0Hz,4H),7.26(d,J＝3.5Hz,2H),7.24(d,J＝7.0Hz,2H),6.88(d,J＝16.0Hz,2H),6.77(d,J＝2.5Hz,2H),6.59(s,2H),4.14(t,J＝7.0Hz,4H),1.86-1.83(m,4H),1.31-1.23(m,36H),0.85(t,J＝6.5Hz,4H)。13C NMR(CDCl3,125MHz)，(ppm):158.7,156.0,137.0,136.6,129.6,127.5,126.9,121.6,120.0,118.4,115.6,111.9,106.7,99.3,58.7,46.7,31.9,30.3,29.6,29.5,29.4,29.3,29.2,27.0,22.7,14.1。MS(ESI,m/z):763.45(M++H)。Anal.calcd for C52H66N4O:C,81.84；H,8.72；N,7.34.Found:C,82.16；H,8.77；N,7.38。
further, the step (1) comprises the following steps:
(11) adding 2, 6-dimethyl-4-pyrone 1 and malononitrile into anhydrous acetic anhydride to form a reaction solution, wherein:
the molar ratio of the 2, 6-dimethyl-4-pyrone 1 to the malononitrile to the acetic anhydride is 1:10: 10;
(12) stirring the reaction solution at 140 ℃ to react for 4 h;
(13) after the reaction is finished, cooling the reaction liquid to room temperature, adding excessive boiling water into the reaction liquid, separating out solids, performing suction filtration, and collecting a crude product;
(14) and (3) purifying the crude product by silica gel column chromatography with petroleum ether/ethyl acetate as an eluent in a volume ratio of 10:1 to obtain an intermediate 2.
Further, the step (2) comprises the following steps:
(21) mixing piperidine and acetonitrile according to the volume ratio of 1:30 to form an excessive mixed solvent;
(22) adding the intermediate 2 and indole aldehydes with different alkyl chains into the mixed solution to form a reaction solution, wherein:
the molar ratio of the intermediate 2 to the indole aldehydes with different alkyl chains is 1: 4;
(23) and heating the reaction solution at 80 ℃ for 24 hours under the protection of nitrogen, and then cooling to room temperature to obtain the dicyanomethylene-4H-pyran derivative.
Further, the indole aldehyde with different alkyl chains in the step (22) is indole aldehyde 4d, which has the following structural formula:
Figure BDA0001363117680000231
characterization of indole aldehyde 4 d:1H NMR(CDCl3,500MHz)，(ppm):10.25(s,1H),7.62(d,J＝7.5Hz,2H),7.35-7.30(m,3H),4.16(t,J＝7.0Hz,2H),1.85-1.82(m,2H),1.30-1.25(m,18H),0.90(t,J＝7.5Hz,3H)。13C NMR(CDCl3,125MHz)，(ppm):192.9,136.7,131.2,128.4,126.9,126.5,120.6,115.6,101.4,46.5,31.8,30.3,29.52,29.45,29.38,29.25,29.11,26.9,22.6,14.0。
still further, the preparation of indole aldehyde 4d comprises the steps of:
(22a) slowly adding 20 molar parts of bromododecane into 423 molar parts of DMSO, and then adding 17 molar parts of indole aldehyde 4a and 25.6 molar parts of KOH into the DMSO to form a mixed solution;
(22b) stirring the mixed solution at room temperature for 12 hours, then adding 5555 mol parts of water, and extracting with dichloromethane;
(22c) the combined dichloromethane organic layers were washed successively with water and brine, and then with anhydrous Na2SO4Drying, distilling the dichloromethane under reduced pressure to dryness to obtain residueThe residue was purified by silica gel column chromatography using petroleum ether/ethyl acetate in a volume ratio of 4:1 to give indole aldehyde 4 d.
The dicyanomethylene-4H-pyran derivative has the characteristic of piezoluminescence discoloration property and is applied to pressure sensors and anti-counterfeiting trademarks.
FIG. 8 is a graph showing solid fluorescence spectra of a raw sample and a ground sample of dicyanomethylene-4H-pyran derivative 7 d. The emission wavelength of the original sample was 590nm, the emission wavelength of the milled sample was 599nm, which was red-shifted by 9 nm. The original sample, which emits yellow fluorescence, was ground to emit yellow fluorescence. The dicyanomethylene-4H-pyran derivative 7d has no piezochromic property because there is no significant change in fluorescence before and after grinding.
Specific example 9
dicyanomethylene-4H-pyran derivatives having the formula:
Figure BDA0001363117680000241
a process for the preparation of dicyanomethylene-4H-pyran derivatives comprising the steps of:
(1) taking 2, 6-dimethyl-4-pyrone 1 as a starting material, and carrying out addition-elimination reaction with malononitrile to obtain an intermediate 2;
(2) and carrying out addition-elimination reaction on the intermediate 2 and indole aldehyde with different alkyl chains to obtain the dicyanomethylene-4H-pyran derivative.
Characterization of dicyanomethylene-4H-pyran derivative 8 a:1H NMR(DMSO-d6,500MHz)，(ppm):11.39(s,2H),8.07(s,2H),7.92(d,J＝16.0Hz,2H),7.63(d,J＝16.5Hz,2H),7.48(d,J＝8.5Hz,2H),7.43(s,2H),7.29(d,J＝16.0Hz,2H),6.81(s,2H),6.54(s,2H)。13C NMR(DMSO-d6,125MHz)，(ppm):159.6,156.2,140.0,137.1,128.0,126.7,126.3,122.5,120.6,116.0,115.5,112.1,105.7,102.1,54.7。MS(ESI,m/z):427.10(M++H)。Anal.calcd for C28H18N4O:C,78.86；H,4.25；N,13.14.Found:C,78.51；H,4.28；N,13.06。
further, the step (1) comprises the following steps:
(11) adding 2, 6-dimethyl-4-pyrone 1 and malononitrile into anhydrous acetic anhydride to form a reaction solution, wherein:
the molar ratio of the 2, 6-dimethyl-4-pyrone 1 to the malononitrile to the acetic anhydride is 1:3: 3;
(12) stirring the reaction solution at 120 ℃ to react for 10 h;
(13) after the reaction is finished, cooling the reaction liquid to room temperature, adding excessive boiling water into the reaction liquid, separating out solids, performing suction filtration, and collecting a crude product;
(14) and (3) purifying the crude product by silica gel column chromatography with petroleum ether/ethyl acetate as an eluent in a volume ratio of 5:1 to obtain an intermediate 2.
Further, the step (2) comprises the following steps:
(21) mixing piperidine and acetonitrile according to the volume ratio of 1:20 to form an excessive mixed solvent;
(22) adding the intermediate 2 and indole aldehydes with different alkyl chains into the mixed solution to form a reaction solution, wherein:
the molar ratio of the intermediate 2 to the indole aldehydes with different alkyl chains is 1: 2;
(23) and heating the reaction solution at 50 ℃ for 48 hours under the protection of nitrogen, and then cooling to room temperature to obtain the dicyanomethylene-4H-pyran derivative.
Further, the indole aldehyde with different alkyl chains in the step (22) is indole aldehyde 5a, which has the following structural formula:
Figure BDA0001363117680000251
the dicyanomethylene-4H-pyran derivative has the characteristic of piezoluminescence discoloration property and is applied to pressure sensors and anti-counterfeiting trademarks.
FIG. 9 is a graph of the solid fluorescence spectra of the original sample of dicyanomethylene-4H-pyran derivative 8a, the ground sample, and the ground sample after fumigation with ethyl acetate vapor. The emission wavelength of the original sample is 608nm, the emission wavelength of the ground sample is 618nm, the red shift is 10nm, and the emission wavelength of the ground sample is recovered to 615nm after fumigation by ethyl acetate steam solvent. The original sample, which emitted orange fluorescence, emitted red fluorescence after grinding, and was again recovered as orange fluorescence by steam fumigation with ethyl acetate. The dicyanomethylene-4H-pyran derivative 8a has a piezochromic property because the fluorescence color changes significantly before and after the grinding.
Detailed description of example 10
dicyanomethylene-4H-pyran derivatives having the formula:
Figure BDA0001363117680000261
a process for the preparation of dicyanomethylene-4H-pyran derivatives comprising the steps of:
(1) taking 2, 6-dimethyl-4-pyrone 1 as a starting material, and carrying out addition-elimination reaction with malononitrile to obtain an intermediate 2;
(2) and carrying out addition-elimination reaction on the intermediate 2 and indole aldehyde with different alkyl chains to obtain the dicyanomethylene-4H-pyran derivative.
Characterization of dicyanomethylene-4H-pyran derivative 8 b:1H NMR(CDCl3,500MHz)，(ppm):7.84(s,2H),7.67(d,J＝16.0Hz,2H),7.48(d,J＝8.5Hz,2H),7.38(d,J＝8.5Hz,2H),7.15(s,2H),6.69(d,J＝16.0Hz,2H),6.58-6.56(m,4H),4.14(t,J＝7.5Hz,4H),1.88-1.82(m,4H),1.40-1.34(m,4H),0.97(t,J＝7.5Hz,6H)。13C NMR(CDCl3,125MHz)，(ppm):159.1,156.2,139.8,137.3,129.2,129.0,126.2,122.6,120.6,115.8,115.3,110.2,106.0,102.2,57.6,46.4,32.4,20.1,13.6。MS(ESI,m/z):539.25(M++H)。Anal.calcd for C36H34N4O:C,80.27；H,6.36；N,10.40.Found:C,79.75；H,6.31；N,10.33。
further, the step (1) comprises the following steps:
(11) adding 2, 6-dimethyl-4-pyrone 1 and malononitrile into anhydrous acetic anhydride to form a reaction solution, wherein:
the molar ratio of the 2, 6-dimethyl-4-pyrone 1 to the malononitrile to the acetic anhydride is 1:3: 3;
(12) stirring the reaction solution at 120 ℃ to react for 10 h;
(13) after the reaction is finished, cooling the reaction liquid to room temperature, adding excessive boiling water into the reaction liquid, separating out solids, performing suction filtration, and collecting a crude product;
(14) and (3) purifying the crude product by silica gel column chromatography with petroleum ether/ethyl acetate as an eluent in a volume ratio of 5:1 to obtain an intermediate 2.
Further, the step (2) comprises the following steps:
(21) mixing piperidine and acetonitrile according to the volume ratio of 1:20 to form an excessive mixed solvent;
(22) adding the intermediate 2 and indole aldehydes with different alkyl chains into the mixed solution to form a reaction solution, wherein:
the molar ratio of the intermediate 2 to the indole aldehydes with different alkyl chains is 1: 2;
(23) and heating the reaction solution at 50 ℃ for 48 hours under the protection of nitrogen, and then cooling to room temperature to obtain the dicyanomethylene-4H-pyran derivative.
Further, the indole aldehyde with different alkyl chains in the step (22) is indole aldehyde 5b, which has the following structural formula:
Figure BDA0001363117680000271
characterization of indole aldehyde 5 b:1H NMR(CDCl3,500MHz)，(ppm):10.00(s,1H),8.12(d,J＝1.0Hz,1H),7.77(dd,3J＝8.5Hz,4J＝1.0Hz,1H),7.39(d,J＝8.5Hz,1H),7.17(d,J＝3.5Hz,1H),6.63(d,J＝3.0Hz,1H),4.11(t,J＝7.0Hz,2H),1.83-1.77(m,2H),1.35-1.28(m,2H),0.93(t,J＝7.5Hz,3H)。13C NMR(CDCl3,125MHz)，(ppm):192.2,139.0,129.6,129.1,128.2,126.3,121.4,109.8,103.0,41.2,32.1,19.9,13.4。
still further, the indole aldehyde 5b preparation comprises the steps of:
s221, slowly adding 10 molar parts of n-butyl bromide into 400 molar parts of DMSO, and then adding 15 molar parts of indole aldehyde 5a and 15 molar parts of KOH into the DMSO to form a mixed solution;
s222, stirring the mixed solution at room temperature for 9 hours, adding 5000 mol parts of water, and extracting with dichloromethane;
s223 the combined dichloromethane organic layers were washed successively with water and brine, and then with anhydrous Na2SO4Drying, distillation of dichloromethane to dryness under reduced pressure gives a residue which is purified by column chromatography on silica gel using petroleum ether/ethyl acetate in a volume ratio of 2:1 to give indole aldehyde 4 b.
The dicyanomethylene-4H-pyran derivative has the characteristic of piezoluminescence discoloration property and is applied to pressure sensors and anti-counterfeiting trademarks.
FIG. 10 is a graph showing solid fluorescence spectra of an original sample and a ground sample of dicyanomethylene-4H-pyran derivative 8 b. The emission wavelength of the original sample was 613nm, the emission wavelength of the milled sample was 614nm, which was red-shifted by 1 nm. The original sample, which emits orange-red fluorescence, is ground to emit orange-red fluorescence. The dicyanomethylene-4H-pyran derivative 8b has no piezochromic property because there is no significant change in fluorescence before and after grinding.
Specific example 11
dicyanomethylene-4H-pyran derivatives having the formula:
Figure BDA0001363117680000281
a process for the preparation of dicyanomethylene-4H-pyran derivatives comprising the steps of:
(1) taking 2, 6-dimethyl-4-pyrone 1 as a starting material, and carrying out addition-elimination reaction with malononitrile to obtain an intermediate 2;
(2) and carrying out addition-elimination reaction on the intermediate 2 and indole aldehyde with different alkyl chains to obtain the dicyanomethylene-4H-pyran derivative.
Characterization of dicyanomethylene-4H-pyran derivative 8 c:1H NMR(CDCl3,500MHz)，(ppm):7.85(s,2H),7.68(d,J＝15.5Hz,2H),7.48(d,J＝8.5Hz,2H),7.38(d,J＝8.5Hz,2H),7.13(s,2H),6.70(d,J＝15.5Hz,2H),6.59(d,J＝16.0Hz,4H),3.94(d,J＝7.5Hz,4H),2.25-2.19(m,2H),0.96(d,J＝6.5Hz,12H)。13C NMR(CDCl3,125MHz)，(ppm):159.1,156.2,139.8,137.6,129.8,129.0,126.3,122.6,120.6,115.8,115.4,110.5,106.0,102.1,57.7,54.3,29.7,20.3。MS(ESI,m/z):539.25(M++H)。Anal.calcd for C36H34N4O:C,80.27；H,6.36；N,10.40.Found:C,79.69；H,6.33；N,10.48。
further, the step (1) comprises the following steps:
(11) adding 2, 6-dimethyl-4-pyrone 1 and malononitrile into anhydrous acetic anhydride to form a reaction solution, wherein:
the molar ratio of the 2, 6-dimethyl-4-pyrone 1 to the malononitrile to the acetic anhydride is 1:40: 40;
(12) stirring the reaction solution at 160 ℃ to react for 1.5 h;
(13) after the reaction is finished, cooling the reaction liquid to room temperature, adding excessive boiling water into the reaction liquid, separating out solids, performing suction filtration, and collecting a crude product;
(14) and (3) purifying the crude product by silica gel column chromatography with petroleum ether/ethyl acetate as an eluent in a volume ratio of 50:1 to obtain an intermediate 2.
Further, the step (2) comprises the following steps:
(21) mixing piperidine and acetonitrile according to the volume ratio of 1:100 to form an excessive mixed solvent;
(22) adding the intermediate 2 and indole aldehydes with different alkyl chains into the mixed solution to form a reaction solution, wherein:
the molar ratio of the intermediate 2 to the indole aldehydes with different alkyl chains is 1: 8;
(23) and heating the reaction solution at 100 ℃ for 12 hours under the protection of nitrogen, and then cooling to room temperature to obtain the dicyanomethylene-4H-pyran derivative.
Further, the indole aldehyde with different alkyl chains in the step (22) is indole aldehyde 5c, which has the following structural formula:
Figure BDA0001363117680000291
characterization of indole aldehyde 5 c:1H NMR(CDCl3,500MHz)，(ppm):10.02(s,1H),8.14(s,1H),7.77(d,J＝8.5Hz,1H),7.40(d,J＝8.5Hz,1H),7.16(d,J＝2.5Hz,1H),6.65(s,1H),3.94(d,J＝7.5Hz,2H),2.24-2.15(m,1H),0.93(d,J＝7.0Hz,6H)。13C NMR(CDCl3,125MHz)，(ppm):192.4,139.6,130.3,129.2,128.2,126.4,121.6,110.1,103.1,54.3,29.7,20.2。
still further, the preparation of indole aldehyde 5c comprises the steps of:
s221, slowly adding 30 molar parts of bromoisobutane into 500 molar parts of DMSO, and then adding 20 molar parts of indolal 5a and 50 molar parts of KOH into the DMSO to form a mixed solution;
s222, stirring the mixed solution at room temperature for 15 hours, adding 6000 mol parts of water, and extracting with dichloromethane;
s223 the combined dichloromethane organic layers were washed successively with water and brine, and then with anhydrous Na2SO4Drying, distillation of dichloromethane to dryness under reduced pressure gives a residue which is purified by column chromatography on silica gel using petroleum ether/ethyl acetate in a volume ratio of 20:1 to give indole aldehyde 4 c.
The dicyanomethylene-4H-pyran derivative has the characteristic of piezoluminescence discoloration property and is applied to pressure sensors and anti-counterfeiting trademarks.
FIG. 11 is a graph showing solid fluorescence spectra of a raw sample and a ground sample of dicyanomethylene-4H-pyran derivative 8 c. The emission wavelengths of the original samples were 588nm and 675nm, the emission wavelengths of the milled samples were changed to 593nm and 657nm, which were red-shifted by 5 nm. The original sample, which emits yellow fluorescence, was ground to emit yellow fluorescence. The dicyanomethylene-4H-pyran derivative 8c has no piezochromic property because there is no significant change in fluorescence before and after grinding.
Detailed description of example 12
dicyanomethylene-4H-pyran derivatives having the formula:
Figure BDA0001363117680000301
a process for the preparation of dicyanomethylene-4H-pyran derivatives comprising the steps of:
(1) taking 2, 6-dimethyl-4-pyrone 1 as a starting material, and carrying out addition-elimination reaction with malononitrile to obtain an intermediate 2;
(2) and carrying out addition-elimination reaction on the intermediate 2 and indole aldehyde with different alkyl chains to obtain the dicyanomethylene-4H-pyran derivative.
Characterization of dicyanomethylene-4H-pyran derivative 8 d:1H NMR(CDCl3,500MHz)，(ppm):7.85(s,2H),7.70(d,J＝15.5Hz,2H),7.49(d,J＝8.5Hz,2H),7.39(d,J＝8.5Hz,2H),7.15(s,2H),6.72(d,J＝16.0Hz,2H),6.63(s,2H),6.57(s,2H),4.14(t,J＝7.0Hz,4H),1.88-1.85(m,4H),1.33-1.26(m,36H),0.86(t,J＝6.5Hz,6H)。13C NMR(CDCl3,125MHz)，(ppm):159.1,156.2,139.9,137.3,129.2,129.1,126.3,122.6,120.7,115.8,115.4,110.3,106.0,102.2,57.8,46.7,31.9,30.3,29.6,29.5,29.4,29.3,29.2,27.0,22.7,14.1。MS(EI,m/z):761.24(M+-H,100),382.23(31％),298.23(78％),207.03(69％),186.10(73％),158.08(67％)。Anal.calcd for C52H66N4O:C,81.84；H,8.72；N,7.34.Found:C,81.23；H,8.69；N,7.29。
further, the step (1) comprises the following steps:
(11) adding 2, 6-dimethyl-4-pyrone 1 and malononitrile into anhydrous acetic anhydride to form a reaction solution, wherein:
the molar ratio of the 2, 6-dimethyl-4-pyrone 1 to the malononitrile to the acetic anhydride is 1:10: 10;
(12) stirring the reaction solution at 140 ℃ to react for 5 h;
(13) after the reaction is finished, cooling the reaction liquid to room temperature, adding excessive boiling water into the reaction liquid, separating out solids, performing suction filtration, and collecting a crude product;
(14) and (3) purifying the crude product by silica gel column chromatography with petroleum ether/ethyl acetate as an eluent in a volume ratio of 10:1 to obtain an intermediate 2.
Further, the step (2) comprises the following steps:
(21) mixing piperidine and acetonitrile according to the volume ratio of 1:50 to form an excessive mixed solvent;
(22) adding the intermediate 2 and indole aldehydes with different alkyl chains into the mixed solution to form a reaction solution, wherein:
the molar ratio of the intermediate 2 to the indole aldehydes with different alkyl chains is 1: 4;
(23) and heating the reaction solution at 80 ℃ for 24 hours under the protection of nitrogen, and then cooling to room temperature to obtain the dicyanomethylene-4H-pyran derivative.
Further, the indole aldehyde with different alkyl chains in the step (22) is indole aldehyde 5d, which has the following structural formula:
Figure BDA0001363117680000311
characterization of indole aldehyde 5 d:1H NMR(CDCl3,500MHz)，(ppm):10.03(s,1H),8.15(s,1H),7.78(dd,3J＝8.5Hz,4J＝1.0Hz,1H),7.41(d,J＝9.0Hz,1H),7.19(d,J＝3.5Hz,1H),6.65(d,J＝3.5Hz,1H),4.14(t,J＝7.0Hz,2H),1.86-1.83(m,2H),1.31-1.24(m,18H),0.88(t,J＝7.0Hz,3H)。13C NMR(CDCl3,125MHz)，(ppm):192.3,139.3,129.7,129.3,128.3,126.5,121.6,109.9,103.2,46.7,31.9,30.2,29.56,29.49,29.42,29.28,29.15,26.9,22.6,14.1。
still further, the preparation of indole aldehyde 5d comprises the steps of:
s221, slowly adding 20 molar parts of bromo-n-dodecane into 423 molar parts of DMSO, and then adding 17 molar parts of indole aldehyde 5a and 25.6 molar parts of KOH into the DMSO to form a mixed solution;
s222, stirring the mixed solution at room temperature for 12 hours, then adding 5555 mol parts of water, and extracting with dichloromethane;
s223 the combined dichloromethane organic layers were washed successively with water and brine, and then with anhydrous Na2SO4Drying, reducing dichloromethaneDistillation under reduced pressure to dryness afforded a residue which was purified by silica gel column chromatography using (4:1 petroleum ether/ethyl acetate) to afford indole aldehyde 4 d.
The dicyanomethylene-4H-pyran derivative has the characteristic of piezoluminescence discoloration property and is applied to pressure sensors and anti-counterfeiting trademarks.
FIG. 12 is a graph showing solid fluorescence spectra of a raw sample and a ground sample of dicyanomethylene-4H-pyran derivative 8 d. The emission wavelength of the original sample is 603nm and 657nm, the emission wavelength of the ground sample is changed into 603nm and 663nm, and the red shift is 6 nm. The original sample, which emitted orange fluorescence, was ground to emit orange fluorescence. The dicyanomethylene-4H-pyran derivative 8d has no piezochromic property because there is no significant change in fluorescence before and after grinding.
The embodiments of the present invention have been described in detail. However, the present invention is not limited to the above-described embodiments, and various changes can be made within the knowledge of those skilled in the art without departing from the spirit of the present invention.

Claims (10)

1. dicyanomethylene-4H-pyran derivatives characterized by the structural formula:
Figure FDA0002514549790000011
2. a process for the preparation of dicyanomethylene-4H-pyran derivatives, characterized in that it comprises the steps of:
(1) under the conditions of acetic anhydride and reflux, 2, 6-dimethyl-4-pyrone 1 is taken as a starting material to perform addition-elimination reaction with malononitrile to obtain an intermediate 2;
(2) in a mixed solution composed of piperidine and acetonitrile, the intermediate 2 and indole aldehyde with different alkyl chains undergo an addition-elimination reaction to obtain a dicyanomethylene-4H-pyran derivative, wherein:
the intermediate 2 reacts with indole aldehyde 3c or indole aldehyde 3d to generate dicyanomethylene-4H-pyran derivative 6c or dicyanomethylene-4H-pyran derivative 6 d;
reacting the intermediate 2 with indole aldehyde 4a or indole aldehyde 4b or indole aldehyde 4c to produce dicyanomethylene-4H-pyran derivative 7a or dicyanomethylene-4H-pyran derivative 7b or dicyanomethylene-4H-pyran derivative 7 c;
the intermediate 2 reacts with indole aldehyde 5a to generate dicyanomethylene-4H-pyran derivative 8 a;
the reaction formula is shown as follows:
Figure FDA0002514549790000021
3. the process for producing a dicyanomethylene-4H-pyran derivative according to claim 2, wherein the step (1) comprises the steps of:
(11) adding 2, 6-dimethyl-4-pyrone 1 and malononitrile into acetic anhydride to form a reaction solution, wherein:
the molar ratio of the 2, 6-dimethyl-4-pyrone 1 to the malononitrile to the acetic anhydride is 1 (3-40) to 3-40;
(12) stirring the reaction solution for reaction for 1.5-10 h under the reflux condition of 120-160 ℃;
(13) after the reaction is finished, cooling the reaction liquid to room temperature, adding excessive boiling water into the reaction liquid, separating out solids, performing suction filtration, and collecting a crude product;
(14) and (3) purifying the crude product by silica gel column chromatography with petroleum ether/ethyl acetate as an eluent in a volume ratio of (5-50): 1 to obtain an intermediate 2.
4. The process for producing a dicyanomethylene-4H-pyran derivative according to claim 2, wherein the step (2) comprises the steps of:
(21) mixing piperidine and acetonitrile according to a volume ratio of 1 (20-100) to form an excessive mixed solvent;
(22) adding the intermediate 2 and indole aldehydes with different alkyl chains into the mixed solution to form a reaction solution, wherein:
the molar ratio of the intermediate 2 to the indole aldehydes with different alkyl chains is 1: (2-8);
(23) and heating the reaction solution to react for 12-48 hours at 50-100 ℃ under the protection of nitrogen, and then cooling to room temperature to obtain the dicyanomethylene-4H-pyran derivative.
5. The method for preparing dicyanomethylene-4H-pyran derivatives according to claim 4, wherein the indole aldehydes having different alkyl chains in the step (22) are indole aldehydes 3c or indole aldehydes 3d, and the structural formula thereof is as follows:
6. the process for preparing dicyanomethylene-4H-pyran derivatives according to claim 5, wherein the preparation of indolal 3c, indolal 3d comprises the steps of:
(221) slowly adding 10-30 molar parts of bromoisobutane or 10-30 molar parts of bromododecane into 400-500 molar parts of DMSO, and then adding 15-20 molar parts of indolal 3a and 15-50 molar parts of KOH into the DMSO to form a mixed solution;
(222) stirring the mixed solution at room temperature for 9-15 h, then adding 5000-6000 mol parts of water, and extracting with dichloromethane;
(223) the combined dichloromethane organic layers were washed successively with water and brine, and then with anhydrous Na2SO4Drying, distilling dichloromethane under reduced pressure to dryness to obtain a residue, purifying the residue by silica gel column chromatography and using petroleum ether/ethyl acetate with a volume ratio of (2-20): 1 to obtain indole aldehyde 3c or indole aldehyde 3d, wherein the chemical formula is as follows:
Figure FDA0002514549790000032
wherein:
Figure FDA0002514549790000033
7. the method for preparing dicyanomethylene-4H-pyran derivatives according to claim 4, wherein the indole aldehydes having different alkyl chains in the step (22) are indole aldehydes 4a or 4b or 4c, which have the following structural formula:
Figure FDA0002514549790000041
8. the process for preparing dicyanomethylene-4H-pyran derivatives according to claim 7, wherein the preparation of indolal 4b, indolal 4c comprises the steps of:
(22a) slowly adding 10-30 molar parts of n-butyl bromide or 10-30 molar parts of iso-butane bromide into 400-500 molar parts of DMSO, and then adding 15-20 molar parts of indole aldehyde 4a and 15-50 molar parts of KOH into the DMSO to form a mixed solution;
(22b) stirring the mixed solution at room temperature for 9-15 h, then adding 5000-6000 mol parts of water, and extracting with dichloromethane;
(22c) the combined dichloromethane organic layers were washed successively with water and brine, and then with anhydrous Na2SO4Drying, distilling dichloromethane under reduced pressure to dryness to obtain a residue, purifying the residue by silica gel column chromatography and using petroleum ether/ethyl acetate with a volume ratio of (2-20): 1 to obtain indole aldehyde 4b or indole aldehyde 4c or indole aldehyde 4d, wherein the chemical formula is as follows:
Figure FDA0002514549790000042
wherein:
Figure FDA0002514549790000043
9. the method for preparing dicyanomethylene-4H-pyran derivatives according to claim 4, wherein the indole aldehyde with different alkyl chains in the step (22) is indole aldehyde 5a, which has the following structural formula:
Figure FDA0002514549790000044
10. the use of dicyanomethylene-4H-pyran derivatives according to any one of claims 1 to 9, in the preparation of pressure sensors, anti-counterfeiting trademarks, wherein:
the dicyanomethylene-4H-pyran derivative has the characteristic of piezoluminescence discoloration property.
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