CN114133395A - Pyrroloquinazolinone skeleton compound with fluorescence characteristic, preparation method and application - Google Patents
Pyrroloquinazolinone skeleton compound with fluorescence characteristic, preparation method and application Download PDFInfo
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Abstract
The invention relates to the technical field of fluorescent characteristic molecular design, in particular to a pyrroloquinazolinone skeleton compound with fluorescent characteristic, a preparation method and application thereof. The structural formula of the compound is shown as follows,
the preparation method comprises the following steps: step one, carrying out Michael addition reaction on 3- (diphenylmethylene amino) -oxindole and an alpha, beta-unsaturated carbonyl compound to generate 3-disubstituted oxindole;secondly, carrying out deprotection and ring closure reaction on the 3-disubstituted oxindole to generate 3,2' -spiro oxindole imine; and step three, carrying out oxidative rearrangement dehydrogenation reaction on the 3,2' -spiro-oxindole imine to generate the pyrroloquinazolinone. The compound has remarkable fluorescence characteristic, and the preparation method can meet the requirements of short synthetic route, cheap and easily-obtained raw materials, strong practicability and high reaction yield, and has good popularization and application prospects.
Description
Technical Field
The invention belongs to the technical field of fluorescent characteristic molecular design, and particularly relates to a pyrroloquinazolinone skeleton compound with fluorescent characteristic, a preparation method and application thereof.
Background
Organic fluorescent substances are a class of compounds having specific optical properties that absorb light of a specific frequency and emit fluorescence longer than the absorption wavelength in the process of electrons returning from an excited state to a ground state. The molecular fluorescence characteristic is widely applied to various fields of dye, OLED, organic small molecular probe and anti-counterfeiting ink. Since the 21 st century, the relationship between the fluorescent characteristic molecular structure and the fluorescent property, the luminescence mechanism and the synthesis of novel fluorescent characteristic molecules are common research hotspots in organic chemistry and materials science.
To date, a wide range of fluorescent-property molecules are used: there are coumarins, rhodamines, spirofluorenes, triarylamines, and the like.
In order to construct specific functions, derivatization and modification are required based on the molecular skeleton, which greatly limits the design thought of people for functional organic fluorescent molecules. In view of this, we have designed and synthesized a new molecular scaffold with fluorescent properties.
Disclosure of Invention
< problems to be solved by the present invention >
A new approach was sought to synthesize molecular scaffolds designed for fluorescent properties.
< technical solution adopted in the present invention >
Aiming at the technical problems, the invention provides a pyrroloquinazolinone skeleton compound with fluorescence characteristic, a preparation method and application thereof.
Specifically, the method comprises the following steps:
first, the present invention provides a pyrroloquinazolinone skeleton compound having fluorescent properties, which is represented by Figure1,
wherein R is1，R2，R3，R4，R5Each independently selected from:
a. a hydrogen atom;
C1-C30 alkyl and substituted alkyl, C1-C30 silyl, C1-C30 haloalkyl, C2-C30 alkenyl, conjugated and unconjugated polyalkenyl, C2-C30 alkynyl and polyalkynyl;
c. halogen, hydroxyl, alkoxy, acyloxy, mercapto, thioether, nitro, carbonyl, carboxyl, ester, substituted or unsubstituted amino, imino, cyano, phosphonate, phosphine, amide, sulfonyl, alkoxycarbonyl, aryloxycarbonyl, alkylaminocarbonyl, arylaminocarbonyl;
d. a substituted or unsubstituted C5-C50 aryl group; a substituted or unsubstituted C5-C50 aryl; a substituted or unsubstituted fused aryl group of C6-C50;
e. substituted or unsubstituted C7-C50 aralkyl; substituted or unsubstituted C7-C50 aralkyloxy; substituted or unsubstituted C7-C50 aralkylthio;
f. chromophoric group: optionally fused and fused rings.
R6Can be selected from:
a. carboxyl, carboxylate group, wherein the alcohol in the carboxylate can be selected from alkyl containing one or more C1-C30, C1-C30 halogenated alkyl, alkenyl containing C2-C30, C2-C30 alkynyl, aryl containing C4-C50, or substituted aryl substituted primary alcohol, secondary alcohol or tertiary alcohol;
b. amides in which the amine may be selected from the group consisting of an alkyl group containing one or more hydrogen atoms, C1-C30, a C1-C30 haloalkyl group, an alkenyl group containing C2-C30, a C2-C30 alkynyl group, an aryl group containing C4-C50, or substituted aryl-substituted ammonia, primary amine or secondary amine;
c. aryl or substituted aryl;
d. a nitrile group;
R7can be selected from:
a. a hydrogen atom;
C1-C30 alkyl, C1-C30 haloalkyl, C2-C30 alkenyl, C2-C30 alkynyl, C4-C50 aryl and substituted aryl;
R8can be selected from:
a. aryl or substituted aryl;
b. chromophoric group: optionally fused and fused.
Secondly, the present invention provides a method for preparing a pyrroloquinazolinone skeleton compound having fluorescent properties, comprising the following main reaction steps, either individually, continuously, separately or without separation, or via a one-pot method:
step one, carrying out Michael addition reaction on 3- (diphenylmethylene amino) -oxindole and an alpha, beta-unsaturated carbonyl compound to generate 3-disubstituted oxindole;
secondly, carrying out deprotection and ring closure reaction on the 3-disubstituted oxindole to generate 3,2' -spiro oxindole imine;
and step three, carrying out oxidative rearrangement dehydrogenation reaction on the 3,2' -spiro-oxindole imine to generate the pyrroloquinazolinone.
The invention provides a pyrroloquinazolinone skeleton compound with fluorescence characteristics, and applications of the pyrroloquinazolinone skeleton compound in (1) organic small-molecule fluorescent probes, (2) fluorescent dyes and fluorescent dye auxiliaries, (3) anti-counterfeiting ink additives and (4) optoelectronic devices.
< advantageous effects achieved by the present invention >
(1) The pyrrolo [1-2c ] quinazolinone framework compound has remarkable fluorescence characteristic.
(2) The preparation method of the pyrrolo [1-2c ] quinazolinone skeleton compound can meet the requirements of short synthetic route, cheap and easily available raw materials, strong practicability and high reaction yield, and has good popularization and application prospects.
Drawings
FIG. 1-FIG. 2 are pyrroloquinazolinone backbone R1The effect on the fluorescence properties;
FIGS. 3-4 are pyrroloquinazolinone backbone R6Influence on the fluorescence characteristic curve;
FIGS. 5-6 are pyrroloquinazolinone backbone R2-R5，R8Influence on the fluorescence characteristic curve.
FIG. 7 is a synthetic route of pyrroloquinazolinone fluorescent compounds;
FIG. 8 is a schematic of the synthesis of intermediate 3 in example 1;
FIG. 9 is a schematic of the synthesis of intermediate 4 in example 1;
FIG. 10 is a schematic diagram showing the synthesis of the fluorescent molecule 1 of example 1;
FIG. 11 is a schematic view of a carboxylic ester hydrolysis reaction in example 7;
FIG. 12 is a schematic diagram of the nitro group reduction reaction in example 8;
FIG. 13 is a scheme showing the synthesis of 1, 3-diphenylpyrroloquinazolinone of example 9.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
< structural formula of pyrroloquinazolinone skeleton Compound >
A pyrroloquinazolinone skeleton compound with fluorescence characteristics, which is shown as Figure1,
wherein R is1，R2，R3，R4，R5Each independently selected from:
a. a hydrogen atom;
C1-C30 alkyl and substituted alkyl, C1-C30 silyl, C1-C30 haloalkyl, C2-C30 alkenyl, conjugated and unconjugated polyalkenyl, C2-C30 alkynyl and polyalkynyl;
c. halogen, hydroxyl, alkoxy, acyloxy, mercapto, thioether, nitro, carbonyl, carboxyl, ester, substituted or unsubstituted amino, imino, cyano, phosphonate, phosphine, amide, sulfonyl, alkoxycarbonyl, aryloxycarbonyl, alkylaminocarbonyl, arylaminocarbonyl;
d. a substituted or unsubstituted C5-C50 aryl group; a substituted or unsubstituted C5-C50 aryl; a substituted or unsubstituted fused aryl group of C6-C50;
e. substituted or unsubstituted C7-C50 aralkyl; substituted or unsubstituted C7-C50 aralkyloxy; substituted or unsubstituted C7-C50 aralkylthio;
f. chromophoric group: optionally fused and fused rings. Such as naphthalene, anthracene, phenanthrene, triarylamine, indole, oxindole, indigo, isoindigo, isatin, coumarin, and the like. Any fused, fused ring includes the following: thiophene, benzothiophene, arylthiophene; carbazole, benzocarbazole, arylcarbazole; pyridine, benzopyridine, isoquinoline, benzoquinoline, aroquinoline, aroisoquinoline; fluorene; furan, benzofuran, arylbenzofuran; pyrrole, indole, arylpyrrole; pyrazole, benzopyrazole, arylpyrazole; oxazole, benzoxazole, arooxazole; isoxazoles, benzisoxazoles, arylisoxazoles; thiazoles, benzothiazoles, arylthiazoles; isothiazole, benzisothiazole, arylisothiazole; imidazole, benzimidazole, arylimidazole; pyrans, benzopyrans, arylpyrans; pyridazine, benzopyridazine, arylpyridazine; pyrimidines, benzopyrimidines, arylpyrimidines; pyrazine, benzopyrazines, arylpyrazines; phenazine, benzophenazine, arylphenazine; thiazines, benzothiazines, arylthiazines; pteridines, benzopteridines, arylpteridines; acridine, benzacridine, and benzacridine; phenothiazine, benzophenothiazine, or arylphenothiazine;
R6can be selected from:
a. carboxyl, carboxylate group, wherein the alcohol in the carboxylate can be selected from alkyl containing one or more C1-C30, C1-C30 halogenated alkyl, alkenyl containing C2-C30, C2-C30 alkynyl, aryl containing C4-C50, or substituted aryl substituted primary alcohol, secondary alcohol or tertiary alcohol;
b. amides in which the amine may be selected from the group consisting of an alkyl group containing one or more hydrogen atoms, C1-C30, a C1-C30 haloalkyl group, an alkenyl group containing C2-C30, a C2-C30 alkynyl group, an aryl group containing C4-C50, or substituted aryl-substituted ammonia, primary amine or secondary amine;
c. aryl or substituted aryl;
d. a nitrile group;
R7can be selected from:
a. a hydrogen atom;
C1-C30 alkyl, C1-C30 haloalkyl, C2-C30 alkenyl, C2-C30 alkynyl, C4-C50 aryl and substituted aryl;
R8can be selected from:
a. aryl or substituted aryl;
b. chromophoric group: optionally fused and fused rings. Such as naphthalene, anthracene, phenanthrene, triarylamine, indole, oxindole, indigo, isoindigo, isatin, coumarin, and the like. Any fused and fused rings are as follows: such as thiophene, benzothiophene, arylthiophene; carbazole, benzocarbazole, arylcarbazole; pyridine, benzopyridine, isoquinoline, benzoquinoline, aroquinoline, aroisoquinoline; fluorene; furan, benzofuran, arylbenzofuran; pyrrole, indole, arylpyrrole; pyrazole, benzopyrazole, arylpyrazole; oxazole, benzoxazole, arooxazole; isoxazoles, benzisoxazoles, arylisoxazoles; thiazoles, benzothiazoles, arylthiazoles; isothiazole, benzisothiazole, arylisothiazole; imidazole, benzimidazole, arylimidazole; pyrans, benzopyrans, arylpyrans; pyridazine, benzopyridazine, arylpyridazine; pyrimidines, benzopyrimidines, arylpyrimidines; pyrazine, benzopyrazines, arylpyrazines; phenazine, benzophenazine, arylphenazine; thiazines, benzothiazines, arylthiazines; pteridines, benzopteridines, arylpteridines; acridine, benzacridine, and benzacridine; phenothiazine, benzophenothiazine or arylphenothiazine.
R in pyrroloquinazolinone backbone compounds1-R8In (1), taking of expressionsAryl substituents include, but are not limited to, C1-C50 alkyl, C1-C30 haloalkyl, C2-C30 alkenyl, C2-C30 alkynyl, halogen, hydroxy, alkoxy, acyloxy, amino, acylated amino, nitro, mercapto, thioether, cyano, carbonyl, carboxyl, ester, amide.
< fluorescence Properties of pyrroloquinazolinone skeleton Compound >
After being irradiated by ultraviolet light or near ultraviolet light, the electrons of the skeleton structure jump to an excited state. Subsequently, radiative transition occurs during the return of the excited state to the ground state, and fluorescence greater than the excitation wavelength is emitted. The inventor simultaneously provides a fluorescence excitation curve and a fluorescence emission curve of a pyrrolo [1-2c ] quinazolinone skeleton compound shown in Figure1 and the yield of the hamamelis quantum of the compound, thereby determining the strongest excitation wavelength range: 260-450nm, the fluorescence emission wavelength range 350-600nm, the solid fluorescence quantum efficiency between 2% and 100%, and the solution quantum efficiency between 15% and 100%.
< relationship between fluorescence emission characteristics and Structure of pyrroloquinazolinone skeleton Compound >
The inventor summarizes the functional molecule of the pyrroloquinazolinone skeleton compound as the fluorescence characteristic and the technical characteristics of the fluorescence emission as follows:
the pyrroloquinazolinone backbone includes quinazolinone structural units and pyrrole ring structural units.
1Influence of the substituents R
Substituent R of quinazolinone structural unit1The influence on the fluorescence emission wavelength of the compound is limited, but the influence on the fluorescence quantum efficiency is very obvious.
To obtain higher fluorescence quantum efficiency, R1Preferably C1-C30 alkyl and substituted alkyl groups, C1-C30 silyl groups, C1-C30 haloalkyl groups, C2-C30 alkenyl groups and conjugated and unconjugated polyalkenyl groups, C2-C30 alkynyl groups and polyalkynyl groups; a substituted or unsubstituted C5-C50 aryl group; a substituted or unsubstituted C5-C50 aryl; the condensed aryl of the substituted or unsubstituted C6-C50 can obtain moderate to excellent fluorescence quantum efficiency.
2 3 4 5Influence of the substituents R, R, R, R
Substituent R of quinazolinone structural unit2，R3，R4，R5The fluorescence emission wavelength and fluorescence quantum efficiency of the pyrroloquinazolinone backbone structure are strongly affected.
R2，R3，R4，R5Preferably a hydrogen atom, an electron-donating substituent such as a hydroxyl group, an alkoxy group, an acyloxy group, a mercapto group, a thioether group, a substituted or unsubstituted amino group, an acylated amine group.
6Influence of the substituents R
Pyrrole ring structural unit substituent R6The influence on the fluorescence emission wavelength is small, and the influence on the fluorescence quantum efficiency is large. To obtain higher fluorescence quantum efficiency, R6Preferably a carboxylic ester group, wherein the alcohol in the carboxylic ester can be selected from the group consisting of alkyl containing one or more C1-C30, C1-C30 haloalkyl, alkenyl containing C2-C30, C2-C30 alkynyl, aryl containing C4-C50, or substituted aryl substituted primary, secondary or tertiary alcohol; amides in which the amine may be selected from the group consisting of an alkyl group containing one or more hydrogen atoms, C1-C30, a C1-C30 haloalkyl group, an alkenyl group containing C2-C30, a C2-C30 alkynyl group, an aryl group containing C4-C50, or substituted aryl-substituted ammonia, primary amine or secondary amine.
7Influence of the substituents R
Substituent R of pyrrole ring structural unit7The fluorescent quantum efficiency and the fluorescence emission wavelength are less influenced, and the fluorescent quantum efficiency and the fluorescence emission wavelength can be selected from alkyl of hydrogen atoms C1-C30, halogenated alkyl of C1-C30, alkenyl of C2-C30, alkynyl of C2-C30, aryl of C4-C50 and substituted aryl.
8Influence of the substituents R
Substituent R of pyrrole ring structural unit8The influence on the fluorescence emission wavelength and the fluorescence quantum efficiency is large. Thus, R8Aryl or substituted aryl groups are preferred, the aryl substituents include, but are not limited to, C1-C50 alkyl, C1-C30 haloalkyl, C2-C30 alkenyl, C2-C30 alkynyl, haloThe amino group of the compound is selected from the group consisting of a hydroxy group, an alkoxy group, an acyloxy group, an amino group, an acylated amino group, a mercapto group, a thioether, an ester group and an amide group. Chromophoric group: any fused ring, such as naphthalene, anthracene, phenanthrene, fluorene, triarylamine, indole, oxindole, indigo, isoindigo, isatin, coumarin, and the like. Any fused ring may be: thiophene, benzothiophene, arylthiophene; carbazole, benzocarbazole, arylcarbazole; pyridine, benzopyridine, isoquinoline, benzoquinoline, aroquinoline, aroisoquinoline; furan, benzofuran, arylbenzofuran; pyrrole, indole, arylpyrrole; pyrazole, benzopyrazole, arylpyrazole; oxazole, benzoxazole, arooxazole; isoxazoles, benzisoxazoles, arylisoxazoles; thiazoles, benzothiazoles, arylthiazoles; isothiazole, benzisothiazole, arylisothiazole; imidazole, benzimidazole, arylimidazole; pyrans, benzopyrans, arylpyrans; pyridazine, benzopyridazine, arylpyridazine; pyrimidines, benzopyrimidines, arylpyrimidines; pyrazine, benzopyrazines, arylpyrazines; phenazine, benzophenazine, arylphenazine; thiazines, benzothiazines, arylthiazines; pteridines, benzopteridines, arylpteridines; acridine, benzacridine, and benzacridine; phenothiazine, benzophenothiazine or arylphenothiazine.
< synthetic route of pyrroloquinazolinone skeleton Compound >
As shown in Scheme1 (fig. 7) (the following Scheme is only schematic and represents only reaction particulars and parts, and is not to be construed or understood as limiting the invention).
< Synthesis procedure of pyrroloquinazolinone skeleton Compound >
The method comprises the following steps: under the action of an alkaline catalyst (Base), 3- (diphenylmethylene amino) -oxoindole 2 and an alpha, beta-unsaturated carbonyl compound 3 (unsaturated ketone, unsaturated keto ester, unsaturated keto amide or unsaturated keto cyanide) are subjected to addition reaction in a solvent S1 at the temperature of T1 under the catalysis of alkali, and a 3-disubstituted oxoindole compound 4 is constructed after T1 hours.
Step two: under the catalysis of Acid (Acid), S2 is used as a solvent, the 3-disubstituted oxoindole compound 4 completes deprotection and ring closure reaction at the temperature of T2, and spiro-3, 2' -pyrroline oxoindole 5 is generated after T2 hours. The reaction in the step is not strictly distinguished, hydrolysis and ring closing can be synchronously carried out under acidic conditions, and the ammonium salt can be separated under proper conditions and then ring closing is carried out step by step. One-pot processes or processes with separate, separate and stepwise reactions are one of the features of the present process.
Step three: under the condition of T3 temperature, S3 is used as a solvent, under the promotion of an oxidant, the 3,2' -dihydropyrrolidine spiro-oxindole 5 undergoes rearrangement dehydrogenation reaction after T3 hours to generate pyrrolo [1-2c ] quinazolinone 1.
The preparation of the framework compound 1 can be independent, continuous, separated or not, or the one-pot method is carried out through the above main reaction steps, the process and the separation and purification can be comprehensively considered according to different reaction conversion results, and the difference results of the reaction of different substrates and target products such as the reaction conversion rate, different combinations of the process and the like are not understood to limit the novelty and the uniqueness of the route and the synthesis method.
< detailed points in the Synthesis procedure of pyrroloquinazolinone skeleton Compound >
In the first step, the first step is carried out,the selection of 3- (diphenylmethylene amino) oxoindole 2 as a synthon is one of the key technologies of the invention. The 3-amino oxindole under the protection of benzophenone has appropriate reaction activity, can perform Michael reaction with an alpha, beta-unsaturated carbonyl compound 3 under the action of base catalysis to construct a 3-position disubstituted oxindole intermediate 4, and has mild reaction conditions and high yield.
The base catalyzing the Michael addition reaction may be selected from inorganic bases and/or organic bases. In particular, the amount of the solvent to be used,
inorganic bases such as ammonia gas, alkali metals, alkali metal oxides and hydroxides, carbonates and bicarbonates of alkali metals, and the like; wherein the alkali metal oxide/hydroxide includes sodium hydroxide/sodium oxide, potassium hydroxide/potassium oxide, calcium hydroxide/calcium oxide, barium hydroxide/barium oxide, lithium hydroxide/lithium oxide, etc.; carbonates and bicarbonates including sodium carbonate/bicarbonate, potassium carbonate/bicarbonate, magnesium carbonate, calcium carbonate, lithium carbonate, cesium carbonate, and the like;
organic bases such as sodium/potassium methoxide, sodium/potassium ethoxide, sodium/potassium tert-butoxide, etc.; alkali metal salts of various C1-C9 alcohols, sodium hydride, sodium amide, etc.; triethylamine, pyridine, piperidine, diisopropylethylamine, 4-Dimethylaminopyridine (DMAP), triethylenediamine (DABCO), 1, 8-diazohetero-bis-spiro [5.4.0] undec-7-ene (DBU), 1, 5-diazabicyclo [4.3.0] non-5-ene (DBN), and cinchona-based tertiary amine compounds. Further, DBU, DABCO are preferable as the catalyst.
In the second step, the first step is carried out,and (3) performing hydrolysis reaction to remove the protecting group and simultaneously closing a ring to form the spiro-3, 2' -pyrroline oxindole 5. The second step is characterized in that the unsaturated carbonyl compound and the deprotected primary amine form an imine in an acidic environment.
The acid can be selected from organic acid or inorganic acid; the organic acid includes acetic acid, alpha mono-or poly-substituted acetic acid such as 2-chloroacetic acid, trichloroacetic acid, trifluoroacetic acid, formic acid, oxalic acid, citric acid or malic acid, sulfonic acid, and pyruvic acid. The inorganic acid comprises hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, p-toluenesulfonic acid, perchloric acid, aqueous hydrochloric acid solution, aqueous sulfuric acid solution, aqueous phosphoric acid solution, aqueous nitric acid solution, aqueous p-toluenesulfonic acid solution or aqueous perchloric acid solution; further, dilute hydrochloric acid, dilute aqueous hydrobromic acid are preferred to achieve the step two conversion process.
In the third step, the first step is carried out,the core is that spiro-3, 2' -pyrroline oxindole 5 undergoes oxidative rearrangement and dehydrogenation to generate pyrrolo [1,2-c]Quinazolinones. The dehydrogenation oxidation rearrangement reaction of the spiro imine is a novel reaction which is not reported, and is also a core reaction step for synthesizing the pyrroloquinazolinone framework compound.
The oxidative dehydrogenation agent can be selected from 2, 3-dichloro-5, 6-dicyan-p-benzoquinone (DDQ), selenium dioxide, manganese dioxide, ammonium ceric nitrate and other common oxidants. Further, the oxidative dehydrogenation reagent is preferably DDQ.
In the above three stepsThe solvents (S1, S2, and S3) include, but are not limited to: water, C1-C8 alcohol solvents, amide solvents, sulfone solvents, aromatic solvents, inert alkane solvents and ether solvents.
Specifically, C1-C8 alcohol solvents such as methanol, ethanol, isopropanol, tert-butanol, n-butanol, etc.; amide-based solvents such as N, N-Dimethylformamide (DMF), N-Diethylformamide (DEF), formamide, N-Dimethylacetamide (DMA), and the like; sulfone solvents such as dimethyl sulfoxide (DMSO), sulfolane, and the like; nitrile solvents such as propionitrile, butyronitrile, benzonitrile, and the like; aromatic hydrocarbon solvents such as toluene, xylene, halogenated benzene, mesitylene, etc.; inert alkane solvents such as dichloromethane, dichloroethane, chloroform, cyclohexane, n-hexane, 1, 2-Dimethoxyethane (DME), and the like; ether solvents such as tetrahydrofuran, dioxane, methyl tert-butyl ether, diethyl ether, etc. Further, water, t-butanol, isopropanol or any ratio combination/mixture thereof is preferred.
The dosage of the solvent is 1: 1-1: 5 of the mass dosage of the raw materials, the influence of the solvent on the reaction is not obvious, the less the dosage is, the less the solubility of the substrate and the product is, the material stirring and heat/temperature control are not facilitated, the larger the dosage is, the lower the equipment efficiency and the longer the reaction time are, the post-treatment efficiency is reduced, and the energy consumption and the post-treatment cost are increased; generally 2-6 times the weight/volume ratio will achieve the desired overall effect.
In the above-mentioned three steps of the method,the suitable temperatures (T1, T2, and T3) are between 20 ℃ and the solvent reflux temperature. The reaction can still be carried out at the temperature of less than 20 ℃, but the reaction time is generally prolonged, the higher the temperature is, the faster the reaction speed is, but the higher the temperature of the reaction system is, the unfavorable for energy and equipment control, and the comprehensive situation is preferably 25-80 ℃. The reaction times (t1, t2 and t3), based on the completion of the substrate reaction, varied with the catalyst, solvent and temperature.
< use of pyrroloquinazolinone skeleton Compound >
The pyrroloquinazolinone skeleton compound has at least the following uses: (1) as the organic small molecule fluorescent probe, the fluorescent probe comprises but is not limited to quantitative or qualitative biological macromolecules, cations, anions and other small molecule compound fluorescent detection probes. (2) The fluorescent dye can be used as a fluorescent dye and a fluorescent dye auxiliary agent for dyeing or whitening clothes and paper. (3) The fluorescent anti-counterfeiting ink is used as an anti-counterfeiting ink additive for fluorescent anti-counterfeiting marks of currency, trademarks and commodities. (4) As optoelectronic devices, electroluminescent or photoluminescent electronic devices are prepared.
< application scenarios of pyrroloquinazolinone framework Compounds >
And a functional fluorescent material containing an independent pyrroloquinazolinone skeleton compound or pyrroloquinazolinone skeleton compound as an additive component. The functions of the fluorescent material include, but are not limited to, the application scenarios described in the foregoing (1) to (4).
< example >
Example 1
A preparation method of a pyrroloquinazolinone skeleton compound comprises the following steps:
in a 50ml single-neck flask, 0.4g (1mmol) of synthon 2a, 0.2g (1.1 mmol) of unsaturated keto ester 3a, and 5ml of methylene chloride were placed. The reaction was carried out at room temperature for 6 hours under the catalysis of 20mg of triethylamine (0.2 mmol). TLC checked for completion and purified by column chromatography (eluent EA: PE ═ 1:5) to afford intermediate 4aa in 78% yield. The synthetic scheme is shown in figure 8.
Step two, 0.592g (1mmol) of intermediate 4aa is dissolved in 10mL of THF solution, 4-7 drops of 1M diluted hydrochloric acid solution are added, and reaction is carried out under magnetic stirring. After 2 hours the reaction was complete as detected by TLC. 1mL of saturated sodium carbonate solution was added to neutralize the hydrochloric acid, and 10mL of distilled water and 10mL of ethyl acetate were added to extract the product. Then 10mL of 2-fold ethyl acetate was added for extraction, and the organic phases were combined and dried. Then, spirocyclic imine 5aa was obtained in a nearly quantitative yield by column chromatography (EA: PE ═ 1: 10). The synthetic scheme is shown in FIG. 9.
Step three, dissolving 0.41g (1mmol) of spiro imine 5aa in 5ml of toluene, adding equivalent weight of DDQ, reacting for 6h at 50 ℃, and detecting the reaction completion by TLC. The reaction system is subjected to wet loading and column chromatography separation and purification, and the fluorescent characteristic substance 1aa is obtained with a yield of 78%. The maximum absorption wavelength of the solid is 376nm, the fluorescence emission wavelength is 414nm, and the quantum yield is 13%. The maximum absorption wavelength of the solution is 378nm, the emission wavelength is 415nm, and the quantum yield is 70%. The synthetic scheme is shown in FIG. 10.
The results of the corresponding formula of the compound are shown below:
Methyl 6-benzyl-5-oxo-1-phenyl-5,6-dihydropyrrolo [1,2-c]quinazoline-3-carboxylate(1aa):
Chemical property：White solid,59％yield,mp:177-179℃,Rf＝0.4(EA:PE＝1:6) 1H NMR(300MHz,CDCl3)δ7.66(dd,J＝8.1,1.5Hz,1H),7.53–7.38 (m,5H),7.34(ddd,J＝8.6,7.2,1.5Hz,1H),7.24(t,J＝7.1Hz,1H),7.03(s, 1H),6.95(ddd,J＝8.2,7.1,1.2Hz,1H),4.26(dd,J＝9.0,6.7Hz,2H),3.96(s, 3H),1.79(p,J＝7.7Hz,2H),1.50(h,J＝7.4Hz,2H),1.01(t,J＝7.3Hz,3H). 13C NMR(75MHz,CDCl3)δ162.0,145.5,135.2,134.0,129.5,128.8, 128.5,127.7,127.3,123.8,122.8,122.6,122.5,121.8,115.9,114.4,52.4,43.8, 29.2,20.1,13.7.HRMS(ESI)m/z calcd for C23H23N2O3+(M+H)+375.1703； Found 375.1703.
example 2
In the first step, the reaction catalyst was replaced by DABCO from triethylamine under the same conditions as in example 1, and the completion of the reaction was detected by TLC after 10 hours of reaction. Column chromatography (eluent EA: PE ═ 1:5) gave intermediate 4aa in 89% yield.
Example 3
In the first step, the catalyst is changed from (Et)3N to K2CO3Otherwise, the reaction was completed by TLC after 24 hours under the same conditions as in example 1. Column chromatography (eluent EA: PE ═ 1:5) afforded intermediate 4aa in 56% yield.
Example 4
In the first step, the reaction substrate 2a was replaced with 2b, and the completion of the reaction was checked by TLC after 6 hours of the reaction under the same reaction conditions as in example 1. Column chromatography (eluent EA: PE ═ 1:5) afforded intermediate 4ba in 86% yield.
Example 5
Intermediate 4aa in example 1 was replaced with 4ba, and the other conditions were the same as in example 1. Spirocyclic imine 5ba was obtained in nearly quantitative yield as well.
Example 6
The spiro imine 5aa in example 1 was replaced with 5ba, and the other conditions were the same. The fluorescent substance 1ba was obtained in a yield of 79%. The maximum absorption wavelength of the solid is 378nm, the fluorescence emission wavelength is 406 nm, and the yield of the hamamatsu quantum is 53%. The maximum absorption wavelength of the liquid is 381nm, the emission wavelength is 414nm, and the yield of the hamaranthus mangostanus quantum is 71%. The results of the corresponding formula of the compound are shown below:
Methyl 6-butyl-5-oxo-1-phenyl-5,6-dihydropyrrolo[1,2-c] quinazoline-3-carboxylate(1ba):
Chemical property：White solid，79％yield，Rf：0.4(PE:EA＝5:1)1H NMR (300MHz,CDCl3)δ7.66(dd,J＝8.1,1.5Hz,1H),7.55–7.39(m,5H),7.34 (ddd,J＝8.6,7.2,1.5Hz,1H),7.24(t,J＝7.1Hz,1H),7.03(s,1H),6.95(ddd, J＝8.2,7.1,1.2Hz,1H),4.26(dd,J＝9.0,6.7Hz,2H),3.96(s,3H),1.79(p,J ＝7.7Hz,2H),1.50(h,J＝7.4Hz,2H),1.01(t,J＝7.3Hz,3H).13C NMR(75 MHz,CDCl3)δ162.0,145.5,135.2,134.0,129.5,128.8,128.5,127.7,127.3, 123.8,122.8,122.6,122.5,121.8,115.9,114.4,52.4,43.8,29.2,20.1, 13.7.HRMS(ESI)m/z calcd for C23H23N2O3 +(M+H)+375.1703,found 375.1703
example 7
Pyrrolo [1,2-c ] quinazolinone compound 1bb bearing carboxylic acid functionality was prepared on the basis of example 6 by dissolving 1ba in 1mL THF, and hydrolyzing under basic conditions with the addition of 0.5mL saturated potassium hydroxide solution. The maximum excitation wavelength of the solution is 382nm, the maximum emission wavelength is 408 nm, and the fluorescence quantum of the solution is 16%. The synthetic scheme is shown in FIG. 11, and the corresponding chemical formula results of the compound are shown as follows:
6-Butyl-5-oxo-1-phenyl-5,6-dihydropyrrolo[1,2-c]quinazoline-3-carboxylic acid (1bb):
Chemical property：White solid,85％yield,mp:184-186℃, Rf＝0.4(EA:PE＝1:6).1H NMR(400MHz,CDCl3)δ15.14(s,1H),7.79(s, 1H),7.72(dd,J＝8.2,1.5Hz,1H),7.53–7.39(m,6H),7.34(dd,J＝8.6,1.1 Hz,1H),7.06(ddd,J＝8.2,7.2,1.1Hz,1H),4.57–4.13(m,2H),1.88– 1.82(m,2H),1.60–1.50(m,2H),1.05(t,J＝7.4Hz,3H).13C NMR(101 MHz,CDCl3)δ158.5,148.4,133.6,131.8,130.5,128.5,128.4,128.1,128.0, 127.3,123.5,123.2,123.0,122.0,115.0,113.8,43.8,28.3,19.1,12.7.HRMS (ESI)m/z calcd for C22H21N2O3+(M+H)+361.1547；Found 361.1545.
example 8
On the basis of successfully constructing 1-p-nitrophenyl-5-carbonyl-6-benzyl pyrrolo [1,2-c ] quinazolinone-3-formate, 1-p-aminophenyl-5-carbonyl-6-benzyl pyrrolo [1,2-c ] quinazolinone-3-formate 1ac is prepared by reducing metal iron powder in a saturated ammonium chloride solution. The maximum excitation wavelength of the solid is 407nm, the emission wavelength is 480nm, and the solid quantum efficiency is 3%; the maximum excitation wavelength of the solution is 398nm, the emission wavelength is 476nm, and the yield of the solid caper quantum is 35%. The synthetic scheme is shown in figure 12.
The results of the corresponding formula of the compound are shown below:
Methyl 1-(4-aminophenyl)-6-benzyl-5-oxo-5,6-dihydro pyrrolo[1,2-c]quinazoline-3-carboxylate(1ac):
Chemicalproperty:White solid,76％yield,mp:159-161℃,Rf＝0.4(EA:PE＝1:6). 1H NMR(300MHz,CDCl3)δ7.77(dd,J＝8.1,1.4Hz,1H),7.37–7.30(m, 4H),7.27(dd,J＝7.0,1.6Hz,3H),7.23-7.12(m,2H),7.05(s,1H),6.86-6.74 (m,2H),5.53(s,2H),3.97(s,3H).13C NMR(75MHz,CDCl3)δ162.2,146.3, 146.1,135.9,134.2,130.5,128.8,128.2,127.5,127.3,126.6,124.8,123.6, 123.5,122.9,122.6,122.4,116.2,115.4,115.2,52.5,47.5,29.6.HRMS(ESI) m/z calcd for C26H22N3O3 +(M+H)+424.1656；Found 424.1655.
example 9
The same conditions were used except that 5ad was used instead of 5aa for the spirocyclic imine in example 1. The fluorescent substance 1ad was obtained in a yield of 79%. The maximum absorption wavelength of the solution is 378nm, the fluorescence emission wavelength is 406 nm, and the yield of the hamamatsu quantum is 53%. The synthetic scheme is shown in FIG. 13, and the corresponding chemical formula results of the compound are shown as follows:
1,3-Diphenylpyrrolo[1,2-c]quinazolin-5(6H)-one(1ad):
Chemicalproperty:White solid,74％yield,mp:181-183℃,Rf＝0.4(EA:PE＝ 1:6).1H NMR(300MHz,DMSO-d6)δ11.35(s,1H),7.56-7.43(m,7H), 7.42-7.30(m,3H),7.30-7.20(m,2H),7.04-6.82(m,1H),6.64(s,1H).13C NMR (75MHz,DMSO)δ145.9,135.7,133.3,133.0,132.0,129.6,129.4,128.9, 127.6,127.5,127.0,126.8,125.2,122.2,122.1,121.5,118.8,115.4,114.7. HRMS(ESI)m/z calcd for C23H17N2O+(M+H)+337.133；Found 337.1334.
example 10
After the three-step reaction was completed by replacing 2a in example 1 with 3-aminooxoindole Schiff base 2c having a tetrahydroquinoline structure, methyl 8-carbonyl-12-phenyl-5, 6-dihydro-4H, 8H-pyrido [3,2,1-ij ] pyrrolo [1,2-c ] quinazolinone-10-carboxylate 1ca was obtained in 46% yield. The maximum excitation wavelength of the solution is 377nm, the maximum emission wavelength is 438nm, and the yield of the hamamatsu quantum is 20%. The results of the corresponding formulae for the compounds are shown below:
Methyl 8-oxo-12-phenyl-5,6-dihydro-4H,8H-pyrido[3,2,1-ij]pyrrolo[1,2-c]quinazoline- 10-carboxylate(1ca):
Chemicalproperty:White solid,46％yield,mp:178-180℃, Rf＝0.4(EA:PE＝1:6)1H NMR(400MHz,CDCl3)δ7.49-7.42(m,5H),7.11(dq,J ＝7.5,1.2Hz,1H),7.03(s,1H),6.86(t,J＝7.7Hz,1H),4.26-4.16(m,2H),3.96 (s,3H),2.93(t,J＝6.2Hz,2H),2.13(p,J＝6.1Hz,2H).13C NMR(101MHz, CDCl3)δ161.2,144.4,134.4,130.4,128.6,127.8,127.5,126.7,126.6,124.2, 122.0,121.5,121.1,120.9,120.7,114.5,51.5,42.5,26.5,19.8.HRMS(ESI) m/z calcd for C22H19N2O3+(M+H)+359.1390；Found 359.1391.
example 11
The 2a in example 1 was replaced with 2-chloroethyl-substituted 3-aminooxoindoxyl Schiff base 2d as the amide nitrogen atom, and the unsaturated methyl keto acid ester 3a was replaced with isopropyl unsaturated keto acid ester 3 e. After the three-step reaction was completed, 1- (2-chloroethyl) -5-carbonyl-1-phenyl-5, 6-dihydropyrrolo [1,2-c ] quinazolinone-3-carboxylic acid isopropyl ester 1de was obtained in 47% yield. The maximum excitation wavelength of the solution is 375nm, the maximum emission wavelength is 412nm, and the yield of the hamamatsu quantum is 66%. The results of the corresponding formula of the compound are shown below:
Isopropyl 6-(2-chloroethyl)-5-oxo-1-phenyl-5,6-dihydropyrrolo[1,2-c]quinazoline-3-carbo xylate(1de):
Chemicalproperty:White solid,47％yield,mp:154-156℃,Rf＝0.4(EA:PE＝1:6). 1H NMR(300MHz,CDCl3)δ7.66(d,J＝8.0Hz,1H),7.52-7.39(m,5H), 7.39-7.25(m,2H),7.02(d,J＝14.5Hz,2H),5.33(p,J＝6.3Hz,1H),4.60(t,J ＝7.4Hz,2H),3.87(t,J＝7.4Hz,2H),1.42(d,J＝6.3Hz,6H).13C NMR(75 MHz,CDCl3)δ160.9,145.5,135.1,133.9,129.5,128.9,128.6,127.9,127.0, 123.9,123.6,123.2,123.0,122.2,116.0,114.1,69.1,45.2,39.3,21.8.HRMS (ESI)m/z calcd for C23H22ClN2O3 +(M+H)+409.1314(Cl35),411.1284(Cl37)； Found 409.1316(Cl35),411.1288(Cl37).
example 12
The 2a in example 1 was replaced with 3-aminooxoindole Schiff base 2e substituted with 2-methyl acetate as the amide nitrogen atom, and the unsaturated ketonic acid methyl ester 3a was replaced with isopropyl ketonate 3 e. After the three-step reaction was completed, 6- (2-acetyl-2-methoxy) -5-carbonyl-1-phenyl-5, 6-dihydropyrrolo [1,2-c ] quinazolinone-3-carboxylic acid isopropyl ester 1ee was obtained in 60% yield. The maximum excitation wavelength of the solution is 369 nm, the maximum emission wavelength is 415nm, and the yield of the hamaranthus mangostanus quantum is 73%. The results of the corresponding formula of the compound are shown below:
Isopropyl 6-(2-methoxy-2-oxoethyl)-5-oxo-1-phenyl-5,6-dihydropyrrolo[1,2-c]quinazoline -3-carboxylate(1ee):
Chemicalproperty:White solid,60％yield,mp:151-153℃, Rf＝0.4(EA:PE＝1:6).1H NMR(300MHz,CDCl3)δ7.70-7.62(m,1H),7.54-7.39 (m,5H),7.37-7.28(m,1H),6.99(dd,J＝15.3,7.5Hz,3H),5.31(p,J＝6.2Hz, 1H),5.08(s,2H),3.79(s,3H),1.40(d,J＝6.3Hz,6H).13C NMR(75MHz, CDCl3)δ168.3,160.8,145.8,135.1,134.1,129.5,128.9,128.6,127.9,127.1, 123.9,123.8,123.2,122.9,122.4,115.9,113.6,69.1,52.7,45.1,21.8.HRMS (ESI)m/z calcd for C24H23N2O5 +(M+H)+419.1602；Found 419.1602.
example 13
After the three-step reaction was completed by replacing 2a in example 1 with 3-aminooxoindole Schiff base 2f substituted with amide nitrogen atom methyl group, methyl 6-methyl-5-carbonyl-1-phenyl-5, 6-dihydropyrrolo [1,2-c ] quinazolinone-3-carboxylate 1fa was obtained in 47% yield. The maximum excitation wavelength of the solution is 380nm, the maximum emission wavelength is 414nm, and the yield of the hamamatsu quantum is 55%. The results of the corresponding formulae for the compounds are shown below:
Methyl 6-methyl-5-oxo-1-phenyl-5,6-dihydropyrrolo[1,2-c]quinazoline-3-carboxylate (1fa):
Chemical property：White solid,47％yield,mp:140-142℃, Rf＝0.4(EA:PE＝1:6)1H NMR(300MHz,CDCl3)δ7.65(dd,J＝8.1,1.4Hz, 1H),7.53-7.39(m,5H),7.36(ddd,J＝8.6,7.2,1.5Hz,1H),7.26(d,J＝2.4Hz, 1H),7.06-6.93(m,2H),3.96(s,3H),3.74(s,3H).13C NMR(75MHz,CDCl3) δ162.1,135.2,135.0,129.6,128.9,128.6,127.8,127.3,123.5,122.9,122.8, 122.0,115.7,114.4,52.5,31.2.HRMS(ESI)m/z calcd for C20H17N2O3 +(M+H)+ 333.1234；Found 333.1240.
example 14
After the three-step reaction was performed by replacing the phenyl group in the unsaturated keto ester 3a in example 1 with p-methoxyphenyl 3f, methyl 6-benzyl-5-carbonyl-1- (4-methoxyphenyl) -5, 6-dihydropyrrolo [1,2-c ] quinazolinone-3-carboxylate 1af was obtained in 53% yield. The maximum excitation wavelength of the solution is 384nm, the maximum emission wavelength is 434nm, and the yield of the hamamatsu quantum is 57%. The results of the corresponding formula of the compound are shown below:
Methyl 1-(4-methoxyphenyl) -6-benzyl-5-oxo-1-phenyl-5,6-dihydropyrrolo[1,2-c]quinazoline-3-carboxylate (1af):
Chemical property：White solid,53％yield,mp:187-189℃, Rf＝0.4(EA:PE＝1:6)1H NMR(300MHz,CDCl3)δ7.67(dd,J＝8.1,1.4Hz,1H), 7.43-7.36(m,2H),7.31(d,J＝3.1Hz,4H),7.22-7.11(m,2H),7.07-6.97(m, 3H),6.93(ddd,J＝8.2,6.8,1.5Hz,1H),5.52(s,2H),3.92(d,J＝21.1Hz,6H). 13C NMR(75MHz,CDCl3)δ162.1,159.3,146.3,135.8,134.2,130.7,128.8, 128.4,127.5,127.3,127.2,126.6,123.6,123.3,122.9,122.7,121.9,116.1, 115.3,114.3,55.3,52.5,47.6.HRMS(ESI)m/z calcd for C27H23N2O4 +(M+H)+439.1652；Found 439.1651.
example 15
And 3g of p-fluorophenyl is replaced by phenyl in the unsaturated keto ester 3a, and after the three-step reaction is completed, methyl 6-benzyl-5-carbonyl-1- (4-fluorophenyl) -5, 6-dihydropyrrolo [1,2-c ] quinazolinone-3-carboxylate 1ag is obtained with 47% yield. The maximum excitation wavelength of the solution is 372nm, the maximum emission wavelength is 415nm, and the yield of the hamaranthus mangostanus quantum is 81%. The results of the corresponding formula of the compound are shown below:
Methyl 1-(4-fluorophenyl)-6-benzyl-5-oxo-1-phenyl-5,6-dihydropyrrolo[1,2-c]quinazoli ne-3-carboxylate(1ag):
Chemical property：Thick solid,63％yield,Rf＝0.4(EA:PE＝1:6)1H NMR(300 MHz,CDCl3)δ7.58(dd,J＝8.0,1.4Hz,1H),7.53-7.39(m,2H),7.32(d,J＝ 6.2Hz,4H),7.25-7.12(m,4H),7.04(d,J＝0.9Hz,1H),6.94(ddd,J＝8.2,7.0, 1.5Hz,1H),5.52(s,2H),3.96(d,J＝1.0Hz,3H).13C NMR(75MHz,CDCl3) δ164.2,162.1,160.9,146.2,135.7,134.3,131.4,131.3,131.1,131.1,128.9, 128.6,127.6,127.5,126.6,123.5,123.0,122.9,122.9,121.0,116.1,115.8,115.5, 52.5,47.7.HRMS(ESI)m/z calcd for C26H20FN2O3 +(M+H)+427.1453；Found 427.1452.
example 16
And (3) replacing phenyl in the unsaturated keto ester 3a with 2-thiophene substituent for 3h, and obtaining 6-benzyl-5-carbonyl-1- (2-thienyl) -5, 6-dihydropyrrolo [1,2-c ] quinazolinone-3-carboxylic acid methyl ester 1ah with 66% yield after completing the three-step reaction. The maximum excitation wavelength of the solution is 380nm, the maximum emission wavelength is 418nm, and the yield of the hamaranthus mangostanus quantum is 12%. The results of the corresponding formula of the compound are shown below:
Methyl 1-(thiophen-2-yl) -6-benzyl-5-oxo-1-phenyl-5,6-dihydropyrrolo[1,2-c]quinazoline-3-carboxylate (1ad):
Chemical property：White solid,66％yield,mp:183-185℃,Rf＝0.4(EA:PE＝1:6). 1H NMR(300MHz,CDCl3)δ7.80(dd,J＝8.1,1.5Hz,1H),7.44(dd,J＝4.6, 1.8Hz,1H),7.36-7.22(m,6H),7.21-7.13(m,3H),7.10(d,J＝1.1Hz,1H), 6.99(ddd,J＝8.2,7.0,1.3Hz,1H),5.52(s,2H),3.96(d,J＝1.5Hz,3H).13C NMR(75MHz,CDCl3)δ161.9,146.0,135.6,134.3,128.9,128.7,127.7, 127.6,127.5,126.6,123.7,123.7,123.2,122.7,115.6,115.3,113.8,52.6,47.6. HRMS(ESI)m/z calcd for C24H19N2O3S+(M+H)+415.1111；Found 415.1113.
example 17
After the three-step reaction is completed by replacing 2g of 5-fluoro-3-aminooxoindole Schiff base with 2a of 3-aminooxoindole, methyl 9-fluoro-6-benzyl-5-carbonyl-1-phenyl-5, 6-dihydropyrrolo [1,2-c ] quinazolinone-3-carboxylate 1ga is obtained in 56% yield. The maximum excitation wavelength of the solution is 384nm, the maximum emission wavelength is 411nm, and the yield of the hamamatsu quantum is 39%. The results of the corresponding formula of the compound are shown below:
Methyl 9-fluoro 6-benzyl-5-oxo-1-phenyl-5,6-dihydropyrrolo[1,2-c]quinazoline-3-carboxylate (1ga):
Chemical property：White solid,56％yield,mp:180-182℃, Rf＝0.4(EA:PE＝1:6).1H NMR(400MHz,CDCl3)δ7.45-7.36(m,5H), 7.27-7.20(m,5H),7.03(dd,J＝9.3,4.6Hz,1H),6.98(s,1H),6.84(ddd,J＝ 9.2,7.6,2.9Hz,1H),5.43(s,2H),3.90(s,3H).13C NMR(101MHz,CDCl3)δ；Found 427.1452.
example 18
And (3) replacing the 3-aminooxoindole Schiff base 2a with 5-methoxy-3-aminooxoindole Schiff base for 2h, and obtaining 9-fluoro-6-benzyl-5-carbonyl-1-phenyl-5, 6-dihydropyrrolo [1,2-c ] quinazolinone-3-carboxylic acid methyl ester 1ha with 47% yield after the three steps of reaction. The maximum excitation wavelength of the solution is 390nm, the maximum emission wavelength is 425nm, and the yield of the hamaranthus retusus quantum is 18%. The results of the corresponding formulae for the compounds are shown below:
Methyl 9-methoxy-6-benzyl-5-oxo-1-phenyl-5,6-dihydropyrrolo[1,2-c]quinazoline-3-ca rboxylate(1ha):
Chemical property：White solid,47％yield,mp:158-160℃,Rf＝0.4(EA:PE＝1:6). 1H NMR(300MHz,CDCl3)δ7.55-7.39(m,5H),7.33-7.27(m,4H),7.13-7.01 (m,3H),6.78(dd,J＝9.2,2.8Hz,1H),5.50(s,2H),3.97(s,3H),3.40(s,3H). 13C NMR(75MHz,CDCl3)δ162.3,155.1,146.1,135.9,135.2,129.9,128.9, 128.8,128.2,128.0,127.5,127.2,126.6,122.9,122.4,122.2,116.7,116.6, 106.5,55.0,52.5,47.7.HRMS(ESI)m/z calcd for C26H21N2O3 +(M+H)+ 409.1547；Found 409.1546.
example 19
And (3) replacing an ester group substituent in the unsaturated keto ester 3b with ethyl 3i, and obtaining 6-benzyl-5-carbonyl-1-phenyl-5, 6-dihydropyrrolo [1,2-c ] quinazolinone-3-carboxylic acid ethyl ester 1ai with the yield of 60% after the three-step reaction is completed. The maximum excitation wavelength of the solution is 380nm, the maximum emission wavelength is 412nm, and the yield of the hamamatsu quantum is 46%. The results of the corresponding formula of the compound are shown below:
Ethyl 6-benzyl-5-oxo-1-phenyl-5,6-dihydropyrrolo[1,2-c]quinazoline-3-carboxylate (1ai):
Chemical property：White solid,60％yield,mp:157-159℃,Rf＝0.4(EA:PE＝1:6). 1H NMR(300MHz,CDCl3)δ7.68(dd,J＝8.0,1.4Hz,1H),7.56-7.42(m,5H), 7.34(d,J＝4.3Hz,4H),7.29-7.15(m,3H),7.10(s,1H),6.93(ddd,J＝8.2,6.6, 1.7Hz,1H),5.54(s,2H),4.47(q,J＝7.1Hz,2H),1.43(t,J＝7.1Hz,3H).13C NMR(75MHz,CDCl3)δ161.6,146.2,135.8,135.2,134.2,129.5,128.8, 128.8,128.4,127.8,127.4,127.2,126.6,123.5,123.3,122.9,122.8,122.1, 115.9,115.2,61.4,47.5,14.2.HRMS(ESI)m/z calcd for C28H25N2O3 +(M+H)+ 437.1860,found 437.1859.
example 20
And (3) replacing an ester group substituent in the unsaturated keto ester 3b with isopropyl 3e, and obtaining 6-benzyl-5-carbonyl-1-phenyl-5, 6-dihydropyrrolo [1,2-c ] quinazolinone-3-carboxylic acid isopropyl ester 1ae with the yield of 59% after the three-step reaction is completed. The maximum excitation wavelength of the solution is 378nm, the maximum emission wavelength is 415nm, and the solution is
Isopropyl
Chemical property：White solid,59％yield,mp:142-144℃,Rf＝0.4(EA:PE＝1:6). 1H NMR(300MHz,CDCl3)δ7.68(dd,J＝8.0,1.4Hz,1H),7.57-7.40(m,5H), 7.34(d,J＝4.3Hz,4H),7.30-7.15(m,3H),7.10(s,1H),6.93(ddd,J＝8.2,6.6, 1.7Hz,1H),5.54(s,2H),4.47(q,J＝7.1Hz,2H),1.43(t,J＝7.1Hz,3H).13C NMR(75MHz,CDCl3)δ161.6,146.2,135.8,135.2,134.2,129.5,128.8, 128.8,128.4,127.8,127.4,127.2,126.6,123.5,123.3,122.9,122.8,122.1, 115.9,115.2,61.4,47.5,14.2.HRMS(ESI)m/z calcd for C28H25N2O3 +(M+H)+ 437.1860；found 437.1859.
< test example >
The effect on the fluorescence characteristic curve was determined for the products 1ba, 1de, 1ee, 1fe, 1aa, 1ca, 1ai, 1ae, 1bb, 1ad, 1ac, 1af, 1ga, 1ha, 1ag, 1 ah.
Wherein, the diagram 1-2 is a pyrroloquinazolinone skeleton R1The effect on the fluorescence properties; FIGS. 3-4 are pyrroloquinazolinone backbone R6Influence on the fluorescence characteristic curve; FIGS. 5-6 are pyrroloquinazolinone backbone R2-R5，R8Influence on the fluorescence characteristic curve.
Wherein, the structural formula of each product is shown as follows:
the above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A pyrroloquinazolinone skeleton compound with fluorescence characteristics is characterized in that the compound is shown as Figure1,
wherein R is1，R2，R3，R4，R5Each independently selected from:
a. a hydrogen atom;
C1-C30 alkyl and substituted alkyl, C1-C30 silyl, C1-C30 haloalkyl, C2-C30 alkenyl, conjugated and unconjugated polyalkenyl, C2-C30 alkynyl and polyalkynyl;
c. halogen, hydroxyl, alkoxy, acyloxy, mercapto, thioether, nitro, carbonyl, carboxyl, ester, substituted or unsubstituted amino, imino, cyano, phosphonate, phosphine, amide, sulfonyl, alkoxycarbonyl, aryloxycarbonyl, alkylaminocarbonyl, arylaminocarbonyl;
d. a substituted or unsubstituted C5-C50 aryl group; a substituted or unsubstituted C5-C50 aryl; a substituted or unsubstituted fused aryl group of C6-C50;
e. substituted or unsubstituted C7-C50 aralkyl; substituted or unsubstituted C7-C50 aralkyloxy; substituted or unsubstituted C7-C50 aralkylthio;
f. a chromophore group; optionally fused or fused rings;
R6can be selected from:
a. carboxyl, carboxylate group, wherein the alcohol in the carboxylate can be selected from alkyl containing one or more C1-C30, C1-C30 halogenated alkyl, alkenyl containing C2-C30, C2-C30 alkynyl, aryl containing C4-C50, or substituted aryl substituted primary alcohol, secondary alcohol or tertiary alcohol;
b. amides in which the amine may be selected from the group consisting of an alkyl group containing one or more hydrogen atoms, C1-C30, a C1-C30 haloalkyl group, an alkenyl group containing C2-C30, a C2-C30 alkynyl group, an aryl group containing C4-C50, or substituted aryl-substituted ammonia, primary amine or secondary amine;
c. aryl or substituted aryl;
d. a nitrile group;
R7can be selected from:
a. a hydrogen atom;
C1-C30 alkyl, C1-C30 haloalkyl, C2-C30 alkenyl, C2-C30 alkynyl, C4-C50 aryl and substituted aryl;
R8can be selected from:
a. aryl or substituted aryl;
b. chromophoric group: optionally fused and fused rings.
2. Pyrroloquinazolinone skeleton compounds having fluorescent properties according to claim 1,
R1can be selected from:
C1-C30 alkyl and substituted alkyl, C1-C30 silyl, C1-C30 haloalkyl, C2-C30 alkenyl and conjugated and unconjugated polyalkenyl, C2-C30 alkynyl and polyalkynyl; a substituted or unsubstituted C5-C50 aryl group; a substituted or unsubstituted C5-C50 aryl; a substituted or unsubstituted fused aryl group of C6-C50;
R2，R3，R4，R5each independently selected from:
hydrogen atom, hydroxyl group, alkoxy group, acyloxy group, sulfhydryl group, thioether group, substituted or unsubstituted amino group, acylated amino group and chromophoric group.
3. Pyrroloquinazolinone skeleton compounds having fluorescent properties according to claim 1,
R6can be selected from:
a carboxylic ester group, wherein the alcohol in the carboxylic ester can be selected from alkyl containing one or more C1-C30, C1-C30 halogenated alkyl, alkenyl containing C2-C30, C2-C30 alkynyl, aryl containing C4-C50, or substituted aryl substituted primary, secondary or tertiary alcohol;
amides in which the amine may be selected from the group consisting of an alkyl group containing one or more hydrogen atoms, C1-C30, a C1-C30 haloalkyl group, an alkenyl group containing C2-C30, a C2-C30 alkynyl group, an aryl group containing C4-C50, or substituted aryl-substituted ammonia, primary amine or secondary amine;
R7can be selected from:
a hydrogen atom, an alkyl group of C1-C30, a halogenated alkyl group of C1-C30, an alkenyl group of C2-C30, an alkynyl group of C2-C30, an aryl group of C4-C50 and a substituted aryl group;
R8can be selected from:
aryl or substituted aryl, chromophoric groups.
4. The pyrroloquinazolinone skeleton compound having fluorescent properties according to any one of claims 1 to 3, characterized in that it can be excited at a wavelength of 260-450nm and emits fluorescence at a wavelength of 350-700 nm.
5. A process for the preparation of pyrroloquinazolinone skeleton compounds with fluorescent properties according to any of claims 1 to 4, characterized in that it comprises the following main reaction steps, either separately, continuously, with or without isolation, or in a one-pot process, via:
step one, carrying out Michael addition reaction on 3- (diphenylmethylene amino) -oxindole and an alpha, beta-unsaturated carbonyl compound to generate 3-disubstituted oxindole;
secondly, carrying out deprotection and ring closure reaction on the 3-disubstituted oxindole to generate 3,2' -spiro oxindole imine;
and step three, carrying out oxidative rearrangement dehydrogenation reaction on the 3,2' -spiro-oxindole imine to generate the pyrroloquinazolinone.
6. The method for preparing pyrroloquinazolinone skeleton compounds with fluorescent properties according to claim 5, wherein the preparation route of said compounds is as shown in Scheme 1:
7. the method for preparing pyrroloquinazolinone skeleton compounds having fluorescent properties according to claim 5 or 6, wherein step one is carried out under the action of basic catalyst, which comprises inorganic base and/or organic base.
8. The method for preparing pyrroloquinazolinone skeleton compounds having fluorescent properties according to claim 5 or 6, wherein step two is carried out under the action of acidic catalyst, wherein the acidic catalyst comprises organic acid and/or inorganic acid.
9. The method for preparing pyrroloquinazolinone skeleton compound having fluorescent properties according to claim 5 or 6, wherein the oxidative dehydrogenation reagent used in the oxidative rearrangement dehydrogenation reaction in step three comprises at least one of 2, 3-dichloro-5, 6-dicyan-p-benzoquinone, selenium dioxide, manganese dioxide, or ceric ammonium nitrate.
10. Use of the pyrroloquinazolinone skeleton compound with fluorescent property according to any one of claims 1 to 4 in (1) organic small molecule fluorescent probes, (2) fluorescent dyes and fluorescent dye auxiliaries, (3) anti-counterfeiting ink additives, and (4) optoelectronic devices.
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| CN115572258A (en) * | 2022-10-08 | 2023-01-06 | 中国科学院成都有机化学有限公司 | C 2 Preparation method of axial chiral biquinoline framework compound |
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