CN108640888B - Double-halogenated salicylaldehyde 3-fluoro-4-morpholinyl aniline Schiff base and preparation method and application thereof - Google Patents
Double-halogenated salicylaldehyde 3-fluoro-4-morpholinyl aniline Schiff base and preparation method and application thereof Download PDFInfo
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Abstract
Double-halogenated salicylaldehyde 3-fluoro-4-morpholinyl aniline Schiff base and preparation method and application thereof, wherein the double-halogenated salicylThe aldehyde condensed 3-fluoro-4-morpholinyl aniline Schiff base is a compound conforming to the following general formula:
wherein, X represents Cl, Br or I. The double-halogenated salicylaldehyde 3-fluoro-4-morpholinyl aniline Schiff base product has the advantages of stable structure, simple preparation method, short reaction time, easiness in industrialization, fluorescent property and potential application value in the aspect of fluorescent materials.
Description
Technical Field
The invention relates to a double-halogenated salicylaldehyde 3-fluoro-4-morpholinyl aniline Schiff base and a preparation method and application thereof, and belongs to the technical field of chemical industry.
Background
Schiff bases are organic compounds containing a-RC ═ N-structure, and are generally obtained by the aldehyde or ketone condensation reaction of amines with carbonyl-containing compounds. Since the first schiff base was synthesized in 1963, the synthesis and bioactivity research of schiff bases and derivatives thereof show a rapid growth trend. The Schiff base compound has a larger pi conjugated system, has strong photoelectric property and can show good photosensitive effect, so that the Schiff base compound can be applied to nonlinear optical materials. In recent years, schiff base compounds have been found to have a certain pharmacological activity, and thus have been the subject of attention again. The Schiff base compounds are relatively easy to synthesize, so that different aldehydes and ketones with carbonyl groups can be flexibly selected to react with various amines, and a plurality of Schiff base compounds with different properties can be developed.
The morpholine ring is a hexatomic heterocyclic ring containing nitrogen and oxygen, and is an important organic chemical raw material. Morpholine and its derivatives have been extensively studied because of their close association with many biological and clinical applications. Due to the structural characteristics of the morpholine and the derivatives thereof, the morpholine and the derivatives thereof have various biological activities and very wide application.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention aims to provide the double-halogenated salicylaldehyde-condensed 3-fluoro-4-morpholinyl aniline Schiff base and the preparation method and application thereof.
In order to achieve the above objects and other related objects, the present invention provides the following technical solutions: the double-halogenated salicylaldehyde 3-fluoro-4-morpholinyl aniline Schiff base is a compound conforming to the following general formula:
wherein, X represents Cl, Br or I.
The preferable technical scheme is as follows: the bis-halogenated salicylaldehyde 3-fluoro-4-morpholinyl aniline Schiff base1H nuclear magnetic resonance spectrum,13C, nuclear magnetic resonance spectrum and mass spectrum analysis, wherein the results are as follows:
when X ═ Cl:1H NMR(400MHz,CDCl3,δ/ppm):14.13(s,1H，OH),8.52(s,1H，CH＝N),6.95-7.45(m,5H,H on benzenes),3.88(t,3JH-H＝4.4Hz,2H,CH2O),3.13(t,3JH-H＝4.4Hz,2H,CH2N)；13C NMR(100MHz,CDCl3δ/ppm) 158.70,156.92, 155.73, 154.45, 141.06, 139.91, 132.54, 129.57, 123.13, 120.25, 118.93, 118.10, 109.07, 66.88, 50.72; mass spectrometry data: MS (M/z),367.3, [ M-1 ]]-；
When X is Br:1H NMR(400MHz,CDCl3,δ/ppm):14.32(s,1H，OH),8.49(s,1H，CH＝N),6.94-7.74(m,5H,H on benzenes),3.88(t,3JH-H＝4.4Hz,2H,CH2O),3.13(t,3JH-H＝4.4Hz,2H,CH2N)；13C NMR(100MHz,CDCl3,δ/ppm):158.39,156.99，154.44，140.88，139.93，137.94，133.26，120.74，118.93，118.12，112.11，110.35，109.06, 66.88, 50.72; mass spectrometry data: MS (M/z),455.2, [ M-1 ]]-；
When X is I:1H NMR(400MHz,CDCl3,δ/ppm):14.56(s,1H，OH),8.40(s,1H，CH＝N),6.94-8.08(m,5H,H on benzenes),3.88(t,3JH-H＝4.4Hz,2H,CH2O),3.13(t,3JH-H＝4.4Hz,2H,CH2N)；13C NMR(100MHz,CDCl3δ/ppm) 160.05,158.06, 156.92, 154.45, 148.92, 140.81, 140.31, 139.88, 120.67, 118.95, 118.10, 109.09, 87.25, 80.00, 66.88, 50.72; mass spectrometry data: MS (M/z),551.1, [ M-1 ]]-。
In order to achieve the above objects and other related objects, the present invention provides the following technical solutions: a preparation method of bis-halogenated salicylaldehyde 3-fluoro-4-morpholinyl aniline Schiff base comprises the steps of reacting bis-halogenated salicylaldehyde and 3-fluoro-4-morpholinyl aniline in an ethanol solution according to a molar mass ratio of 1:1 for 30-40min to obtain a crude product, and washing the crude product with ethanol to obtain the bis-halogenated salicylaldehyde 3-fluoro-4-morpholinyl aniline Schiff base.
In order to achieve the above objects and other related objects, the present invention provides the following technical solutions: an application of double-halogenated salicylaldehyde 3-fluoro-4-morpholinyl aniline Schiff base, wherein the double-halogenated salicylaldehyde 3-fluoro-4-morpholinyl aniline Schiff base is used as a fluorescent material.
In order to achieve the above objects and other related objects, the present invention provides the following technical solutions: a fluorescent material comprising a compound corresponding to the general formula:
wherein, X represents Cl, Br or I.
Due to the application of the technical scheme, compared with the prior art, the invention has the advantages that:
1. the Schiff base has high purity, simple preparation method, short reaction time, easy industrialization, fluorescent property and potential application value in the aspect of fluorescent materials.
2. The preparation method has mild reaction conditions and can react at normal temperature; the product is easy to purify, and only needs to be filtered and dried after being washed by ethanol; the yield is high and is between 83 and 92 percent.
3. The double-halogenated salicylaldehyde 3-fluoro-4-morpholinyl aniline Schiff base product has a stable structure and exists in a crystal structure below 180 ℃.
Drawings
FIG. 1 shows bis-chloro-salicylaldehyde 3-fluoro-4-morpholinylaniline Schiff base1H NMR spectrum.
FIG. 2 shows bis-chloro-salicylaldehyde 3-fluoro-4-morpholinylaniline Schiff base13C NMR spectrum.
FIG. 3 is a MS spectrum of dichloro salicylaldehyde 3-fluoro-4-morpholinyl aniline Schiff base.
FIG. 4 shows bis-bromosalicylaldehyde 3-fluoro-4-morpholinylaniline Schiff base1H NMR spectrum.
FIG. 5 shows bis-bromosalicylaldehyde 3-fluoro-4-morpholinylaniline Schiff base13C NMR spectrum.
FIG. 6 is a MS spectrum of dibromo salicylaldehyde 3-fluoro-4-morpholinyl aniline Schiff base.
FIG. 7 is a scheme of bis-iodo salicylaldehyde 3-fluoro-4-morpholinylaniline Schiff base1H NMR spectrum.
FIG. 8 is a scheme of bis-iodo salicylaldehyde 3-fluoro-4-morpholinylaniline Schiff base13C NMR spectrum.
FIG. 9 is a MS spectrum of bis-iodo salicylaldehyde 3-fluoro-4-morpholinylaniline Schiff base.
FIG. 10 is a fluorescence spectrum of bis-halogenated salicylaldehyde 3-fluoro-4-morpholinylaniline Schiff base.
Detailed Description
The following description of the embodiments of the present invention is provided for illustrative purposes, and other advantages and effects of the present invention will become apparent to those skilled in the art from the present disclosure.
Please refer to fig. 1 to 10. It should be understood that the structures, ratios, sizes, and the like shown in the drawings and described in the specification are only used for matching with the disclosure of the specification, so as to be understood and read by those skilled in the art, and are not used to limit the conditions under which the present invention can be implemented, so that the present invention has no technical significance, and any structural modification, ratio relationship change, or size adjustment should still fall within the scope of the present invention without affecting the efficacy and the achievable purpose of the present invention. In addition, the terms "upper", "lower", "left", "right", "middle" and "one" used in the present specification are for clarity of description, and are not intended to limit the scope of the present invention, and the relative relationship between the terms and the terms is not to be construed as a scope of the present invention.
Example 1: double-halogenated salicylaldehyde 3-fluoro-4-morpholinyl aniline Schiff base and preparation method and application thereof
0.95g (5mmo1) of 3, 5-dichlorosalicylaldehyde and 0.98g (5mmol) of 3-fluoro-4-morpholinylaniline dissolved in 15mL of absolute ethyl alcohol are added into a 100mL three-necked flask and stirred for 30min at normal temperature; cooling, separating out solid, filtering, washing with ethanol, and drying to obtain 1.70g of transparent solid yellow green solid, namely the bischlorosalicylaldehyde 3-fluoro-4-morpholinyl aniline Schiff base. Yield: 92 percent; melting point: 201 ℃ and 202 ℃. Warp beam1H nuclear magnetic resonance spectrum,13The results of the C NMR and mass spectrometry are shown in FIGS. 1 to 3.
1H NMR(400MHz,CDCl3,δ/ppm):14.13(s,1H，OH),8.52(s,1H，CH＝N),6.95-7.45(m,5H,H on benzenes),3.88(t,3JH-H＝4.4Hz,2H,CH2O),3.13(t,3JH-H＝4.4Hz,2H,CH2N)；
13C NMR(100MHz,CDCl3,δ/ppm):158.70,156.92，155.73，154.45，141.06，139.91，132.54，129.57，123.13，120.25，118.93，118.10，109.07，66.88，50.72；
Mass spectrometry data: MS (M/z),367.3, [ M-1 ]]-。
From the above information, the structural formula was finally determined as follows:
X＝Cl。
example 2: double-halogenated salicylaldehyde 3-fluoro-4-morpholinyl aniline Schiff base and preparation method and application thereof
1.39g (5mmo1) of 3, 5-dibromo salicylaldehyde and 0.98g (5mmol) of 3-fluoro-4-morpholinylaniline dissolved in 15mL of absolute ethanol are added into a 100mL three-necked flask, and the mixture is stirred for 30min at normal temperature; cooling, separating out solid, filtering, washing with ethanol, and drying to obtain orange solid 1.89g, which is the dibromo salicylaldehyde 3-fluoro-4-morpholinyl aniline Schiff base. Yield: 83 percent; melting point: 191-192 ℃. Warp beam1H nuclear magnetic resonance spectrum,13The results of C NMR and mass spectrometry are shown in FIGS. 4 to 6.
1H NMR(400MHz,CDCl3,δ/ppm):14.32(s,1H，OH),8.49(s,1H，CH＝N),6.94-7.74(m,5H,H on benzenes),3.88(t,3JH-H＝4.4Hz,2H,CH2O),3.13(t,3JH-H＝4.4Hz,2H,CH2N)；
13C NMR(100MHz,CDCl3,δ/ppm):158.39,156.99，154.44，140.88，139.93，137.94，133.26，120.74，118.93，118.12，112.11，110.35，109.06，66.88，50.72；
Mass spectrometry data: MS (M/z),455.2, [ M-1 ]]-。
From the above information, the structural formula was finally determined as follows:
X＝Br。
example 3: double-halogenated salicylaldehyde 3-fluoro-4-morpholinyl aniline Schiff base and preparation method and application thereof
1.87g (5mmo1) of 3, 5-diiodosalicylaldehyde and 0.98g (5mmol) of 3-fluoro-4-morpholinylaniline dissolved in 15mL of absolute ethanol are added into a 100mL three-necked flask and stirred for 40min at normal temperature; cooling and precipitatingAnd (3) filtering the solid, washing the solid with ethanol, and drying the solid to obtain 2.45g of a blood red solid, namely the diiodo salicylaldehyde-condensed 3-fluoro-4-morpholinyl aniline Schiff base. Yield: 89 percent; melting point: 181 ℃ and 183 ℃. Warp beam1H nuclear magnetic resonance spectrum,13The results of C NMR and mass spectrometry are shown in FIGS. 7 to 9.
1H NMR(400MHz,CDCl3,δ/ppm):14.56(s,1H，OH),8.40(s,1H，CH＝N),6.94-8.08(m,5H,H on benzenes),3.88(t,3JH-H＝4.4Hz,2H,CH2O),3.13(t,3JH-H＝4.4Hz,2H,CH2N)；
13C NMR(100MHz,CDCl3,δ/ppm):160.05,158.06，156.92，154.45，148.92，140.81，140.31，139.88，120.67，118.95，118.10，109.09，87.25，80.00，66.88，50.72；
Mass spectrometry data: MS (M/z),551.1, [ M-1 ]]-。
From the above information, the structural formula was finally determined as follows:
X＝I。
example 4: application of double-halogenated salicylaldehyde 3-fluoro-4-morpholinyl aniline Schiff base
Testing the solid fluorescence spectra of the three Schiff bases prepared in examples 1-3 at room temperature; as shown in fig. 10, it can be seen from fig. 10 that the fluorescence spectra of all three schiff base compounds are at about 580nm, and the maximum emission fluorescence spectrum is at 574nm when X ═ Cl is present; when X is Br, the maximum emission fluorescence spectrum is 581 nm; when X is I, the emission spectrum is maximal at 598 nm; the fluorescence spectrum intensity is obviously influenced by heavy atom effect, and the intensity is reduced from Cl-Br-I in sequence. Therefore, the three bis-halogenated salicylaldehyde 3-fluoro-4-morpholinyl aniline Schiff bases prepared in the embodiments 1 to 3 can be used as fluorescent materials.
Example 5: fluorescent material
The preparation method is characterized in that double iodo salicylaldehyde 3-fluoro-4-morpholinyl aniline Schiff base, double bromo salicylaldehyde 3-fluoro-4-morpholinyl aniline Schiff base and double chloro salicylaldehyde 3-fluoro-4-morpholinyl aniline Schiff base are mixed according to the weight ratio of 1: 1: 2, and mixing the components in a mass ratio.
The foregoing embodiments are merely illustrative of the principles and utilities of the present invention and are not intended to limit the invention. Any person skilled in the art can modify or change the above-mentioned embodiments without departing from the spirit and scope of the present invention. Accordingly, it is intended that all equivalent modifications or changes which can be made by those skilled in the art without departing from the spirit and technical spirit of the present invention be covered by the claims of the present invention.
Claims (2)
1. The double-halogenated salicylaldehyde 3-fluoro-4-morpholinyl aniline Schiff base is characterized in that: the double halogenated salicylaldehyde 3-fluoro-4-morpholinyl aniline Schiff base is a compound conforming to the following general formula:
wherein, X represents Cl or Br.
2. The use of the bis-halogenated salicylaldehyde 3-fluoro-4-morpholinylaniline schiff base of claim 1, wherein: the double-halogenated salicylaldehyde 3-fluoro-4-morpholinyl aniline Schiff base is used as a fluorescent material.
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