CN107382978B - 1, 4-dihydropyridine derivative and preparation method and application thereof - Google Patents
1, 4-dihydropyridine derivative and preparation method and application thereof Download PDFInfo
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- YNGDWRXWKFWCJY-UHFFFAOYSA-N 1,4-Dihydropyridine Chemical class C1C=CNC=C1 YNGDWRXWKFWCJY-UHFFFAOYSA-N 0.000 title claims abstract description 114
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 150000001875 compounds Chemical class 0.000 claims abstract description 40
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 claims abstract description 22
- GXHFUVWIGNLZSC-UHFFFAOYSA-N meldrum's acid Chemical compound CC1(C)OC(=O)CC(=O)O1 GXHFUVWIGNLZSC-UHFFFAOYSA-N 0.000 claims abstract description 17
- VSYFZULSKMFUJJ-UHFFFAOYSA-N 2,6-dimethylpyran-4-one Chemical compound CC1=CC(=O)C=C(C)O1 VSYFZULSKMFUJJ-UHFFFAOYSA-N 0.000 claims abstract description 16
- BGNGWHSBYQYVRX-UHFFFAOYSA-N 4-(dimethylamino)benzaldehyde Chemical compound CN(C)C1=CC=C(C=O)C=C1 BGNGWHSBYQYVRX-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000001953 recrystallisation Methods 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 10
- 238000006482 condensation reaction Methods 0.000 claims abstract description 6
- 238000003379 elimination reaction Methods 0.000 claims abstract description 6
- 238000010534 nucleophilic substitution reaction Methods 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 239000012046 mixed solvent Substances 0.000 claims description 57
- 239000000243 solution Substances 0.000 claims description 51
- 238000006243 chemical reaction Methods 0.000 claims description 38
- 239000011259 mixed solution Substances 0.000 claims description 32
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 30
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 30
- 238000002156 mixing Methods 0.000 claims description 23
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 20
- 238000001816 cooling Methods 0.000 claims description 20
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 10
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 claims description 10
- 239000012043 crude product Substances 0.000 claims description 10
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 238000007710 freezing Methods 0.000 claims description 5
- 230000008014 freezing Effects 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 238000010992 reflux Methods 0.000 claims 1
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 11
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 8
- 230000002776 aggregation Effects 0.000 description 7
- 238000004220 aggregation Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 238000002189 fluorescence spectrum Methods 0.000 description 4
- 238000004746 piezoluminescence Methods 0.000 description 3
- 238000002845 discoloration Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000000171 quenching effect Effects 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical group CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 238000005166 mechanoluminescence Methods 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
- C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
- C07D405/04—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
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- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- C09K9/00—Tenebrescent materials, i.e. materials for which the range of wavelengths for energy absorption is changed as a result of excitation by some form of energy
- C09K9/02—Organic tenebrescent materials
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01L—MEASURING FORCE, STRESS, TORQUE, WORK, MECHANICAL POWER, MECHANICAL EFFICIENCY, OR FLUID PRESSURE
- G01L1/00—Measuring force or stress, in general
- G01L1/24—Measuring force or stress, in general by measuring variations of optical properties of material when it is stressed, e.g. by photoelastic stress analysis using infrared, visible light, ultraviolet
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01L—MEASURING FORCE, STRESS, TORQUE, WORK, MECHANICAL POWER, MECHANICAL EFFICIENCY, OR FLUID PRESSURE
- G01L11/00—Measuring steady or quasi-steady pressure of a fluid or a fluent solid material by means not provided for in group G01L7/00 or G01L9/00
- G01L11/02—Measuring steady or quasi-steady pressure of a fluid or a fluent solid material by means not provided for in group G01L7/00 or G01L9/00 by optical means
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- C09K2211/1088—Heterocyclic compounds characterised by ligands containing oxygen as the only heteroatom
Abstract
The invention belongs to the field of organic chemical synthesis and application, and relates to a 1, 4-dihydropyridine derivative, a preparation method and application thereof. A process for the preparation of a 1, 4-dihydropyridine derivative comprising the steps of: (1) preparing an initial sample of the 1, 4-dihydropyridine derivative; (2) carrying out different recrystallization modes on an initial sample of the 1, 4-dihydropyridine derivative to obtain three different crystalline compounds I-y, I-o and I-r, wherein the step (1) comprises the following steps: (11) taking 2, 6-dimethyl-4-pyrone 1 as an initial raw material, and carrying out addition-elimination reaction with Meldrum's acid to generate an intermediate 2; (12) the intermediate 2 and 4-dimethylaminobenzaldehyde are subjected to condensation reaction to generate an intermediate 3; (13) and (3) carrying out nucleophilic substitution reaction on the intermediate 3 and ethylamine to synthesize an initial sample of the 1, 4-dihydropyridine derivative.
Description
Technical Field
The invention belongs to the field of organic chemical synthesis and application, and relates to a 1, 4-dihydropyridine derivative, a preparation method and application thereof.
Background
The piezoluminescent material is also called mechanoluminescence material or triboluminescent material, is an important intelligent material, and has great application potential in the fields of fluorescent sensors, pressure sensors, anti-counterfeiting marks and the like.
Organic molecules with aggregation-induced emission properties generally have a distorted molecular conformation and thus can well overcome the fluorescence quenching effect due to pi-pi stacking caused by aggregation (see the literature: chem. Commun.,2001, 1740-1741; J. Mater. chem.,2001,11,2974-2978), expanding their range of application as fluorescent materials in film-forming or solid-state forms. Another noteworthy advantage of organic molecules with aggregation-induced emission properties is that the molecular structure can be designed to adjust intermolecular forces and stacking patterns of molecules in an aggregated state or a solid state, so that different crystalline structures can be formed, and distinct solid-state fluorescence can be emitted, thereby making it possible to obtain a piezochromic material with multiple color changes (see J.Phys.chem.C., 2012,116, 21967-. The development of new color-changing materials with aggregation-induced emission, polycrystal state and piezoluminescence has received great attention from the scientific and industrial fields.
1, 4-dihydropyridine is an excellent traditional structural unit for constructing various fluorescent compounds, but the derivative thereof is easy to cause the phenomenon of fluorescence quenching in an aggregation state due to a pi-pi stacking effect so far, so that the application of the derivative as a fluorescent material in a film forming or solid state form is limited, and a piezoluminescence color-changing material based on the 1, 4-dihydropyridine structural unit is rarely reported. In order to overcome the defect that the common 1, 4-dihydropyridine derivative has low solid-state luminous efficiency, the invention designs and synthesizes the 1, 4-dipyridine derivative which has aggregation-induced luminescence, polycrystal state and piezoluminescence discoloration properties.
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 disclose a 1, 4-dihydropyridine derivative having aggregation-induced emission, polymorphic state and piezochromic color change properties simultaneously. The second purpose of the invention is to disclose a preparation method of 1, 4-dihydropyridine derivatives. The third purpose of the invention is to disclose the application of the 1, 4-dihydropyridine 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: 1, 4-dihydropyridine derivative having the following structural formula (I):
the 1, 4-dihydropyridine derivative of the formula (I) is subjected to different recrystallization modes to obtain three different crystalline compounds I-y, I-o and I-r, wherein the three crystalline compounds have the same structural formula.
A process for the preparation of a 1, 4-dihydropyridine derivative comprising the steps of:
(1) preparation of initial sample of 1, 4-dihydropyridine derivative
(11) Taking 2, 6-dimethyl-4-pyrone 1 as an initial raw material, and carrying out addition-elimination reaction with Meldrum's acid to generate an intermediate 2;
(12) the intermediate 2 and 4-dimethylaminobenzaldehyde are subjected to condensation reaction to generate an intermediate 3;
(13) the intermediate 3 and ethylamine are subjected to nucleophilic substitution reaction to synthesize an initial sample of the 1, 4-dihydropyridine derivative;
the reaction formula is shown as follows:
(2) three different crystalline compounds I-y, I-o and I-r are obtained by carrying out different recrystallization modes on an initial sample of the 1, 4-dihydropyridine derivative.
Further, the step (11) comprises the steps of:
(111) adding 2, 6-dimethyl-4-pyrone 1 and Meldrum's acid into acetic anhydride to form a mixed solution, wherein:
2, 6-dimethyl-4-pyrone 1: meldrum's acid: the molar ratio of the acetic anhydride is 1 (1.2-3) to 2-15;
(112) and (3) placing the mixed solution in the air, heating and reacting for 1.5-10 h at 120-160 ℃, and cooling to room temperature to obtain an intermediate 2.
Further, the step (12) includes the steps of:
(121) acetonitrile and piperidine are mixed according to the volume ratio of (3-30): 1 forming an excess of mixed solvent;
(122) adding the intermediate 2 and 4-dimethylaminobenzaldehyde to the mixed solvent to form a mixed solution, wherein:
the molar ratio of the intermediate 2 to the 4-dimethylaminobenzaldehyde is 1: (2-8);
(123) and heating and stirring the mixed solution at 50-100 ℃ under the protection of nitrogen for reaction for 12-48 h, and cooling to room temperature to obtain an intermediate 3.
Further, the step (13) includes the steps of:
(131) mixing ethylamine and acetonitrile according to the volume ratio of 1 (3-8) to form a mixed solution;
(132) dissolving the intermediate 3 in the mixed solution formed in the step (131) to form a reaction solution, stirring the reaction solution at 50-100 ℃ to react for 12-48 h, cooling the reaction solution to room temperature after the reaction is finished, freezing the reaction solution at-5-15 ℃ for 1-4 h, separating out solids, filtering to obtain a crude product, washing the crude product with methanol for 3-5 times, and drying to obtain an initial sample of the 1, 4-dihydropyridine derivative.
Further, the step (2) comprises the following steps:
(21) mixing n-hexane and acetone according to the volume ratio of (2-5) to 1 to form a mixed solvent;
(22) dissolving an initial sample of the 1, 4-dihydropyridine derivative in the mixed solvent formed in the step (21) to form a solution, heating the solution to 60 ℃, maintaining the temperature for 2-5 minutes, and cooling to room temperature to obtain a crystalline compound I-y emitting yellow fluorescence, wherein:
the molar ratio of the initial sample of the 1, 4-dihydropyridine derivative to the mixed solvent was 1: (500-3000).
Further, the step (2) comprises the following steps:
(21) mixing toluene and acetone according to the volume ratio of (2-5) to 1 to form a mixed solvent;
(22) dissolving an initial sample of the 1, 4-dihydropyridine derivative in the mixed solvent formed in the step (21) to form a solution, placing the solution in the air, and volatilizing completely to obtain a crystalline compound I-o emitting orange fluorescence, wherein:
the molar ratio of the initial sample of the 1, 4-dihydropyridine derivative to the mixed solvent was 1: (500-3000).
Further, the step (2) comprises the following steps:
(21) mixing ethyl acetate and chloroform according to the volume ratio of (2-5) to 1 to form a mixed solvent;
(22) dissolving an initial sample of the 1, 4-dihydropyridine derivative in the mixed solvent formed in step (21) to form a solution, placing the solution in air, and volatilizing completely to emit a crystalline compound I-r which emits red fluorescence, wherein:
the molar ratio of the initial sample of the 1, 4-dihydropyridine derivative to the mixed solvent was 1: (500-3000).
Further, the 1, 4-dihydropyridine derivative is applied to pressure sensors and anti-counterfeiting marks.
The invention provides a novel organic fluorescent molecule based on a 1, 4-dihydropyridine unit, a preparation method and application thereof, wherein 4-dimethylamino benzene, Meldrum's acid and a 1, 4-dihydropyridine structure unit are introduced into the field of organic solid luminescent materials, crystalline compounds emitting different colors of fluorescence can be obtained by using different recrystallization methods for the organic solid luminescent materials, and the three crystalline compounds are further found to have the property of pressure-induced fluorescence discoloration, so that the organic fluorescent molecule is very suitable for preparing pressure sensors, anti-counterfeiting trademarks and other fields, and has good scientific research value and industrial application potential.
Drawings
FIG. 1 is a graph showing fluorescence emission spectra of an initial sample (10.0. mu. mol/L) of a 1, 4-dihydropyridine derivative in a mixed solvent of pure dimethyl sulfoxide and water having a water content of 80%. The compound is weak in light emission in dimethyl sulfoxide, emits orange fluorescence when the water volume content is 80%, has the emission wavelength of 598nm, and has the fluorescence enhancement 11 times that of pure dimethyl sulfoxide.
FIG. 2 is a graph showing the tendency of change in fluorescence intensity of an initial sample (10.0. mu. mol/L) of a 1, 4-dihydropyridine derivative in a mixed solvent of dimethyl sulfoxide and water having a water content of 0 to 90%.
FIG. 3 is a fluorescence emission spectrum of a sample of 1, 4-dihydropyridine derivative (I-y) under light pressure and heavy pressure. The emission wavelength of the crystalline compound I-y is 577nm, yellow fluorescence is emitted, the emission wavelength of a sample after being lightly ground is 565nm, and the fluorescence does not change color; after the mixture is ground by force, the emission wavelength is changed into 619nm, and the fluorescence color is changed into red.
FIG. 4 is a fluorescence emission spectrum of a sample of 1, 4-dihydropyridine derivative (I-o) under light pressure and heavy pressure. The emission wavelength of the crystalline compound I-o is 598nm, orange fluorescence is emitted, the emission wavelength of a sample is changed into 570nm after the sample is lightly ground, and the fluorescence color is changed from orange to yellow; after the mixture is ground by force, the emission wavelength is changed into 619nm, and the fluorescence color is changed into red.
FIG. 5 is a fluorescence emission spectrum of a sample of 1, 4-dihydropyridine derivative (I-r) under light pressure and heavy pressure. The emission wavelength of the crystalline compound I-r is 633nm, red fluorescence is emitted, the emission wavelength of a sample is changed into 566nm after the sample is lightly ground, and the fluorescence color is changed into yellow from red; after further force milling, the emission wavelength was 618nm and the fluorescence color was red.
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
1, 4-dihydropyridine derivative having the following structural formula (I):
the 1, 4-dihydropyridine derivative of the formula (I) is subjected to different recrystallization modes to obtain three different crystalline compounds I-y, I-o and I-r, wherein the three crystalline compounds have the same structural formula.
A process for the preparation of a 1, 4-dihydropyridine derivative comprising the steps of:
(1) preparation of initial sample of 1, 4-dihydropyridine derivative
(11) Taking 2, 6-dimethyl-4-pyrone 1 as an initial raw material, and carrying out addition-elimination reaction with Meldrum's acid to generate an intermediate 2;
(12) the intermediate 2 and 4-dimethylaminobenzaldehyde are subjected to condensation reaction to generate an intermediate 3;
(13) the intermediate 3 and ethylamine are subjected to nucleophilic substitution reaction to synthesize an initial sample of the 1, 4-dihydropyridine derivative;
the reaction formula is shown as follows:
(2) three different crystalline compounds I-y, I-o and I-r are obtained by carrying out different recrystallization modes on an initial sample of the 1, 4-dihydropyridine derivative.
The structural formula of the initial sample of the 1, 4-dihydropyridine derivative is completely the same as that of crystalline compounds I-y, I-o and I-r.
Further, the step (11) comprises the steps of:
(111) adding 2, 6-dimethyl-4-pyrone 1 and Meldrum's acid into acetic anhydride to form a mixed solution, wherein:
2, 6-dimethyl-4-pyrone 1: meldrum's acid: the molar ratio of acetic anhydride is 1:1.2: 2;
(112) and (3) placing the mixed solution in the air, heating the mixed solution at 120 ℃ for reaction for 10h, and cooling the mixed solution to room temperature to obtain an intermediate 2.
Further, the step (12) includes the steps of:
(121) mixing acetonitrile and piperidine according to a volume ratio of 3:1 forming an excess of mixed solvent;
(122) adding the intermediate 2 and 4-dimethylaminobenzaldehyde to the mixed solvent to form a mixed solution, wherein:
the molar ratio of the intermediate 2 to the 4-dimethylaminobenzaldehyde is 1: 2;
(123) and heating and stirring the mixed solution at 50 ℃ for reaction for 48 hours under the protection of nitrogen, and cooling to room temperature to obtain an intermediate 3.
Further, the step (13) includes the steps of:
(131) mixing ethylamine and acetonitrile according to the volume ratio of 1:3 to form a mixed solution;
(132) dissolving the intermediate 3 in the mixed solution formed in the step (131) to form a reaction solution, stirring the reaction solution at 50 ℃ for 48 hours, cooling the reaction solution to room temperature after the reaction is finished, freezing the reaction solution at-5 ℃ for 4 hours, separating out solids, filtering to obtain a crude product, washing the crude product with methanol for 3 times, and drying to obtain an initial sample of the 1, 4-dihydropyridine derivative.
Characterization of 1, 4-dihydropyridine derivatives:1H NMR(CDCl3,500MHz):δ8.98(s,2H),7.43(d,J＝8.0Hz,4H),7.32(d,J＝15.5Hz,2H),6.80(d,J＝15.5Hz,2H),6.72(d,J＝7.5Hz,4H),4.27(q,J＝6.5Hz,2H),3.03(s,12H),1.72(s,6H),1.51(t,J＝7.0Hz,3H).13C NMR(CDCl3,125MHz):δ165.5,151.3,148.6,140.3,130.4,129.0,123.2,117.5,113.4,112.0,100.9,81.8,45.0,40.2,26.5,14.8.
further, the step (2) comprises the following steps:
(21) mixing n-hexane and acetone according to the volume ratio of 2:1 to form a mixed solvent;
(22) dissolving an initial sample of the 1, 4-dihydropyridine derivative in the mixed solvent formed in step (21) to form a solution, then heating the solution to 60 ℃, maintaining the temperature for 2 minutes, and cooling to room temperature to obtain a crystalline compound I-y emitting yellow fluorescence, wherein:
the molar ratio of the initial sample of the 1, 4-dihydropyridine derivative to the mixed solvent was 1: 500.
further, the 1, 4-dihydropyridine derivative is applied to pressure sensors and anti-counterfeiting marks.
Specific example 2
Substantially the same as in example 1, except that:
the step (2) comprises the following steps:
(21) mixing n-hexane and acetone according to the volume ratio of 5:1 to form a mixed solvent;
(22) dissolving an initial sample of the 1, 4-dihydropyridine derivative in the mixed solvent formed in step (21) to form a solution, then heating the solution to 60 ℃, maintaining the temperature for 5 minutes, and cooling to room temperature to obtain a crystalline compound I-y emitting yellow fluorescence, wherein:
the molar ratio of the initial sample of the 1, 4-dihydropyridine derivative to the mixed solvent was 1: 3000.
specific example 3
Substantially the same as in example 1, except that:
the step (2) comprises the following steps:
(21) mixing n-hexane and acetone according to a volume ratio of 3:1 to form a mixed solvent;
(22) dissolving an initial sample of the 1, 4-dihydropyridine derivative in the mixed solvent formed in step (21) to form a solution, then heating the solution to 60 ℃, maintaining the temperature for 3 minutes, and cooling to room temperature to obtain a crystalline compound I-y emitting yellow fluorescence, wherein:
the molar ratio of the initial sample of the 1, 4-dihydropyridine derivative to the mixed solvent was 1: 1500.
specific example 4
1, 4-dihydropyridine derivative having the following structural formula (I):
the 1, 4-dihydropyridine derivative of the formula (I) is subjected to different recrystallization modes to obtain three different crystalline compounds I-y, I-o and I-r, wherein the three crystalline compounds have the same structural formula.
A process for the preparation of a 1, 4-dihydropyridine derivative comprising the steps of:
(1) preparation of initial sample of 1, 4-dihydropyridine derivative
(11) Taking 2, 6-dimethyl-4-pyrone 1 as an initial raw material, and carrying out addition-elimination reaction with Meldrum's acid to generate an intermediate 2;
(12) the intermediate 2 and 4-dimethylaminobenzaldehyde are subjected to condensation reaction to generate an intermediate 3;
(13) the intermediate 3 and ethylamine are subjected to nucleophilic substitution reaction to synthesize an initial sample of the 1, 4-dihydropyridine derivative;
the reaction formula is shown as follows:
(2) three different crystalline compounds I-y, I-o and I-r are obtained by carrying out different recrystallization modes on an initial sample of the 1, 4-dihydropyridine derivative.
Further, the step (11) comprises the steps of:
(111) adding 2, 6-dimethyl-4-pyrone 1 and Meldrum's acid into acetic anhydride to form a mixed solution, wherein:
2, 6-dimethyl-4-pyrone 1: meldrum's acid: the molar ratio of acetic anhydride is 1:3: 15;
(112) and (3) placing the mixed solution in the air, heating and reacting for 1.5h at the temperature of 160 ℃, and cooling to room temperature to obtain an intermediate 2.
Further, the step (12) includes the steps of:
(121) mixing acetonitrile and piperidine according to a volume ratio of 30: 1 forming an excess of mixed solvent;
(122) adding the intermediate 2 and 4-dimethylaminobenzaldehyde to the mixed solvent to form a mixed solution, wherein:
the molar ratio of the intermediate 2 to the 4-dimethylaminobenzaldehyde is 1: 8;
(123) and heating and stirring the mixed solution at 100 ℃ for reaction for 12 hours under the protection of nitrogen, and cooling to room temperature to obtain an intermediate 3.
Further, the step (13) includes the steps of:
(131) mixing ethylamine and acetonitrile according to the volume ratio of 1:8 to form a mixed solution;
(132) dissolving the intermediate 3 in the mixed solution formed in the step (131) to form a reaction solution, stirring the reaction solution at 100 ℃ for reaction for 12 hours, cooling the reaction solution to room temperature after the reaction is finished, freezing the reaction solution at-15 ℃ for 1 hour, separating out solids, filtering to obtain a crude product, washing the crude product with methanol for 5 times, and drying to obtain an initial sample of the 1, 4-dihydropyridine derivative.
Further, the step (2) comprises the following steps:
(21) mixing toluene and acetone according to the volume ratio of 5:1 to form a mixed solvent;
(22) dissolving an initial sample of the 1, 4-dihydropyridine derivative in the mixed solvent formed in the step (21) to form a solution, placing the solution in the air, and volatilizing completely to obtain a crystalline compound I-o emitting orange fluorescence, wherein:
the molar ratio of the initial sample of the 1, 4-dihydropyridine derivative to the mixed solvent was 1: 3000.
further, the 1, 4-dihydropyridine derivative is applied to pressure sensors and anti-counterfeiting marks.
Specific example 5
Substantially the same as in example 4, except that:
the step (2) comprises the following steps:
(21) mixing toluene and acetone according to the volume ratio of 2:1 to form a mixed solvent;
(22) dissolving an initial sample of the 1, 4-dihydropyridine derivative in the mixed solvent formed in the step (21) to form a solution, placing the solution in the air, and volatilizing completely to obtain a crystalline compound I-o emitting orange fluorescence, wherein:
the molar ratio of the initial sample of the 1, 4-dihydropyridine derivative to the mixed solvent was 1: 500.
specific example 6
Substantially the same as in example 4, except that:
the step (2) comprises the following steps:
(21) mixing toluene and acetone according to the volume ratio of 3:1 to form a mixed solvent;
(22) dissolving an initial sample of the 1, 4-dihydropyridine derivative in the mixed solvent formed in the step (21) to form a solution, placing the solution in the air, and volatilizing completely to obtain a crystalline compound I-o emitting orange fluorescence, wherein:
the molar ratio of the initial sample of the 1, 4-dihydropyridine derivative to the mixed solvent was 1: 2000.
specific example 7
1, 4-dihydropyridine derivative having the following structural formula (I):
the 1, 4-dihydropyridine derivative of the formula (I) is subjected to different recrystallization modes to obtain three different crystalline compounds I-y, I-o and I-r, wherein the three crystalline compounds have the same structural formula.
A process for the preparation of a 1, 4-dihydropyridine derivative comprising the steps of:
(1) preparation of initial sample of 1, 4-dihydropyridine derivative
(11) Taking 2, 6-dimethyl-4-pyrone 1 as an initial raw material, and carrying out addition-elimination reaction with Meldrum's acid to generate an intermediate 2;
(12) the intermediate 2 and 4-dimethylaminobenzaldehyde are subjected to condensation reaction to generate an intermediate 3;
(13) the intermediate 3 and ethylamine are subjected to nucleophilic substitution reaction to synthesize an initial sample of the 1, 4-dihydropyridine derivative;
the reaction formula is shown as follows:
(2) three different crystalline compounds I-y, I-o and I-r are obtained by carrying out different recrystallization modes on an initial sample of the 1, 4-dihydropyridine derivative.
Further, the step (11) comprises the steps of:
(111) adding 2, 6-dimethyl-4-pyrone 1 and Meldrum's acid into acetic anhydride to form a mixed solution, wherein:
2, 6-dimethyl-4-pyrone 1: meldrum's acid: the molar ratio of acetic anhydride is 1:2: 5;
(112) and (3) placing the mixed solution in the air, heating and reacting for 5h at the temperature of 140 ℃, and cooling to room temperature to obtain the intermediate 2.
Further, the step (12) includes the steps of:
(121) mixing acetonitrile and piperidine according to a volume ratio of 15: 1 forming an excess of mixed solvent;
(122) adding the intermediate 2 and 4-dimethylaminobenzaldehyde to the mixed solvent to form a mixed solution, wherein:
the molar ratio of the intermediate 2 to the 4-dimethylaminobenzaldehyde is 1: 4;
(123) and heating and stirring the mixed solution at 50-100 ℃ under the protection of nitrogen for reaction for 12-48 h, and cooling to room temperature to obtain an intermediate 3.
Further, the step (13) includes the steps of:
(131) mixing ethylamine and acetonitrile according to the volume ratio of 1:4 to form a mixed solution;
(132) and (3) dissolving the intermediate 3 in the mixed solution formed in the step (131) to form a reaction solution, stirring the reaction solution at 80 ℃ for 24 hours for reaction, cooling the reaction solution to room temperature after the reaction is finished, freezing the reaction solution at-10 ℃ for 2 hours, separating out solids, filtering to obtain a crude product, washing the crude product with methanol for 4 times, and drying to obtain an initial sample of the 1, 4-dihydropyridine derivative.
Further, the step (2) comprises the following steps:
(21) mixing ethyl acetate and chloroform according to the volume ratio of 3:1 to form a mixed solvent;
(22) dissolving an initial sample of the 1, 4-dihydropyridine derivative in the mixed solvent formed in step (21) to form a solution, placing the solution in air, and volatilizing completely to emit a crystalline compound I-r which emits red fluorescence, wherein:
the molar ratio of the initial sample of the 1, 4-dihydropyridine derivative to the mixed solvent was 1: 2000.
further, the 1, 4-dihydropyridine derivative is applied to pressure sensors and anti-counterfeiting marks.
Specific example 8
Substantially the same as in example 7, except that:
the step (2) comprises the following steps:
(21) mixing ethyl acetate and chloroform according to the volume ratio of 2:1 to form a mixed solvent;
(22) dissolving an initial sample of the 1, 4-dihydropyridine derivative in the mixed solvent formed in step (21) to form a solution, placing the solution in air, and volatilizing completely to emit a crystalline compound I-r which emits red fluorescence, wherein:
the molar ratio of the initial sample of the 1, 4-dihydropyridine derivative to the mixed solvent was 1: 500.
specific example 9
Substantially the same as in example 7, except that:
the step (2) comprises the following steps:
(21) mixing ethyl acetate and chloroform according to the volume ratio of 5:1 to form a mixed solvent;
(22) dissolving an initial sample of the 1, 4-dihydropyridine derivative in the mixed solvent formed in step (21) to form a solution, placing the solution in air, and volatilizing completely to emit a crystalline compound I-r which emits red fluorescence, wherein:
the molar ratio of the initial sample of the 1, 4-dihydropyridine derivative to the mixed solvent was 1: 3000.
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 (5)
- A process for producing a 1, 4-dihydropyridine derivative, which comprises the steps of:(1) preparation of initial sample of 1, 4-dihydropyridine derivative(11) Taking 2, 6-dimethyl-4-pyrone 1 as an initial raw material, and carrying out addition-elimination reaction with Meldrum's acid to generate an intermediate 2;(12) the intermediate 2 and 4-dimethylaminobenzaldehyde are subjected to condensation reaction to generate an intermediate 3;(13) the intermediate 3 and ethylamine are subjected to nucleophilic substitution reaction to synthesize an initial sample of the 1, 4-dihydropyridine derivative;the reaction formula is shown as follows:
(2) an initial sample of the 1, 4-dihydropyridine derivative was subjected to different recrystallization regimes to give three different crystalline compounds I-y, I-o and I-r, wherein:recrystallization of crystalline compounds I-y comprises the following steps:(21) mixing n-hexane and acetone according to the volume ratio of (2-5) to 1 to form a mixed solvent;(22) dissolving an initial sample of the 1, 4-dihydropyridine derivative in the mixed solvent formed in the step (21) to form a solution, heating the solution to 60 ℃, maintaining the temperature for 2-5 minutes, and cooling to room temperature to obtain a crystalline compound I-y emitting yellow fluorescence, wherein:the molar ratio of the initial sample of the 1, 4-dihydropyridine derivative to the mixed solvent was 1: (500-3000);recrystallization of crystalline compounds I-o comprises the following steps:s21, mixing toluene and acetone according to the volume ratio of (2-5) to 1 to form a mixed solvent;s22, dissolving an initial sample of the 1, 4-dihydropyridine derivative in the mixed solvent formed in the step S21 to form a solution, placing the solution in the air, and obtaining a crystalline compound I-o emitting orange fluorescence after complete volatilization, wherein:the molar ratio of the initial sample of the 1, 4-dihydropyridine derivative to the mixed solvent was 1: (500-3000);recrystallization of crystalline compounds I-r comprises the following steps:step21, mixing ethyl acetate and chloroform according to the volume ratio of (2-5) to 1 to form a mixed solvent;step22, dissolving an initial sample of the 1, 4-dihydropyridine derivative in the mixed solvent formed in Step21 to form a solution, placing the solution in air, and obtaining a crystalline compound I-r emitting red fluorescence after complete volatilization, wherein:the molar ratio of the initial sample of the 1, 4-dihydropyridine derivative to the mixed solvent was 1: (500-3000). - 2. The process for producing a 1, 4-dihydropyridine derivative as claimed in claim 1, wherein the step (11) comprises the steps of:(111) adding 2, 6-dimethyl-4-pyrone 1 and Meldrum's acid into acetic anhydride to form a mixed solution, wherein:2, 6-dimethyl-4-pyrone 1: meldrum's acid: the molar ratio of the acetic anhydride is 1 (1.2-3) to 2-15;(112) and (3) placing the mixed solution in air, heating and reacting for 1.5-10 h under the reflux condition of 120-160 ℃, and cooling to room temperature to obtain an intermediate 2.
- 3. The process for producing a 1, 4-dihydropyridine derivative as claimed in claim 1, wherein the step (12) comprises the steps of:(121) acetonitrile and piperidine are mixed according to the volume ratio of (3-30): 1 forming an excess of mixed solvent;(122) adding the intermediate 2 and 4-dimethylaminobenzaldehyde to the mixed solvent to form a mixed solution, wherein:the molar ratio of the intermediate 2 to the 4-dimethylaminobenzaldehyde is 1: (2-8);(123) and heating and stirring the mixed solution at 50-100 ℃ under the protection of nitrogen for reaction for 12-48 h, and cooling to room temperature to obtain an intermediate 3.
- 4. The process for producing a 1, 4-dihydropyridine derivative as claimed in claim 1, wherein the step (13) comprises the steps of:(131) mixing ethylamine and acetonitrile according to the volume ratio of 1 (3-8) to form a mixed solution;(132) dissolving the intermediate 3 in the mixed solution formed in the step (131) to form a reaction solution, stirring the reaction solution at 50-100 ℃ to react for 12-48 h, cooling the reaction solution to room temperature after the reaction is finished, freezing the reaction solution at-5-15 ℃ for 1-4 h, separating out solids, filtering to obtain a crude product, washing the crude product with methanol for 3-5 times, and drying to obtain an initial sample of the 1, 4-dihydropyridine derivative.
- 5. The use of the 1, 4-dihydropyridine derivative according to any of claims 1 to 4 in the preparation of pressure sensors and anti-counterfeiting labels.
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| Aggregation-Induced Fluorescence Emissinon Properties of Dicyanomethylene-1,4-dihydropyridine Derivatives;Hui Li et al.;《J.Phys.Chem.C》;20150306;第119卷;第6737-6748页 * |
| Theoretical investigation of electro-luminescent properties in red emission DCM,DCJ,RED and DAD derivatives;Bo-Cheng Wang et al.;《Journal of Molecular Structure》;20030415;第107卷;第3942-3951页 * |
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