CN108456188B - 7-diethylamino-4-hydroxymethyl coumarin derivative, preparation method and application thereof as nano fragrance precursor - Google Patents
7-diethylamino-4-hydroxymethyl coumarin derivative, preparation method and application thereof as nano fragrance precursor Download PDFInfo
- Publication number
- CN108456188B CN108456188B CN201810437558.4A CN201810437558A CN108456188B CN 108456188 B CN108456188 B CN 108456188B CN 201810437558 A CN201810437558 A CN 201810437558A CN 108456188 B CN108456188 B CN 108456188B
- Authority
- CN
- China
- Prior art keywords
- diethylamino
- hydroxymethylcoumarin
- coumarin
- derivative
- acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
- C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D311/04—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring
- C07D311/06—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2
- C07D311/08—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2 not hydrogenated in the hetero ring
- C07D311/16—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2 not hydrogenated in the hetero ring substituted in position 7
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
- C11B9/00—Essential oils; Perfumes
- C11B9/0069—Heterocyclic compounds
- C11B9/0073—Heterocyclic compounds containing only O or S as heteroatoms
- C11B9/008—Heterocyclic compounds containing only O or S as heteroatoms the hetero rings containing six atoms
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
Abstract
The invention discloses a 7-diethylamino-4-hydroxymethyl coumarin derivative, the structural formula of which is shown in formula I:
wherein: r1Is at least one of alkyl, alkoxy and substituted aryl. The preparation method of the 7-diethylamino-4-hydroxymethyl coumarin derivative provided by the invention is simple, has fewer synthesis steps and low raw material cost, and is expected to be further widely applied to the field of slow release of perfumes.
Description
Technical Field
The invention relates to the technical field of perfumes, in particular to a 7-diethylamino-4-hydroxymethyl coumarin derivative, a preparation method and application of the derivative as a nano perfume precursor.
Background
The perfume and essence are widely applied to daily necessities (food, textile, leather, paper making, cosmetics, washing products, printing ink, medicines and the like), and become important factors influencing the development of national economy and the improvement of the quality of life of people.
The traditional essence and flavor are blended into a mixture for use, the components are complex, loss is easy to occur due to different volatility, and deterioration is caused due to the action of pH, light, heat, oxygen and the like in the environment, so that the perfuming effect of the applied product is influenced to a great extent. Therefore, the protection of perfume molecules by a certain means, so that the perfume molecules exist stably under general conditions and can be released stably under certain conditions (acidity, temperature, illumination and the like), thereby achieving the purpose of slow release of the perfume, is one of the hot spots of research in the field of current flavors and fragrances (Materials Chemistry and Physics 1999,58, 128).
The existing method for releasing the controlled release perfume molecules is to load the controlled release perfume molecules into high molecular compounds (such as vesicles and the like), so that a new idea is provided for the slow release application of the perfume, the stability and the slow release performance of the perfume are improved, but the method is complex in preparation and undefined in structure, and the repeatability of the method is limited, so that the further application of the perfume is influenced. Therefore, the source innovation is carried out from the molecular structure design, the chemical modification and modification innovation design is carried out on the molecular structure of the spice, and the latent aroma molecules with different thresholds are constructed by applying the concept of the latent aroma molecules. Based on the linker of environmental response and the chemical conditions of bionic cutting, the structure-activity relationship between the substituent effect of latent fragrance molecules and the functional groups of fragrance molecules is explored, the speed and the concentration of fragrance release are researched, and the possibility of fundamentally solving fragrance synergy and long-acting property is provided (daily chemical industry 2007,37, 47-49).
Until now, there is no perfume pro-fragrance body with commercial application value. Therefore, there is a great need in the art for a fragrance vehicle with promising commercial application.
Disclosure of Invention
The first object of the present invention is to provide a 7-diethylamino-4-hydroxymethylcoumarin derivative which is an excellent photo-controlled flavorant or fragrance-forming agent useful for fluorescence detection.
Another object of the present invention is to provide a method for preparing the 7-diethylamino-4-hydroxymethylcoumarin derivative.
It is a further object of the present invention to provide a use of said 7-diethylamino-4-hydroxymethylcoumarin derivatives in the perfumery industry.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the invention provides a 7-diethylamino-4-hydroxymethyl coumarin derivative in a first aspect, which has a structural formula shown in formula I:
wherein: r1Is at least one of alkyl, alkoxy and substituted aryl.
Preferably, in the compound shown in the formula I, R1Is at least one of C1-C10 alkyl, C1-C10 alkoxy and substituted aryl.
More preferably, in the compound shown in the formula I, R1One selected from the following groups:
in the definition of formula I given above, the terms used in the collection are generally defined as follows:
alkyl means a straight or branched chain saturated aliphatic hydrocarbon group containing 1 to 10 carbon atoms, for example: methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, methylthio, ethylthio and the like.
Alkoxy means a straight or branched chain alkoxy group containing 1 to 10 carbon atoms. For example: methoxy, ethoxy, n-propoxy, isopropoxy, and the like.
Aryl means a mono-, di-or tricyclic hydrocarbon compound in which at least one ring is aromatic and each ring contains up to 7 carbon atoms, for example phenyl, naphthyl, anthracenyl, biphenyl or indenyl.
Another aspect of the present invention provides a preparation method of the 7-diethylamino-4-hydroxymethylcoumarin derivative, comprising the steps of:
in a proper solvent, 7-diethylamino-4-methylcoumarin reacts with an oxidant in a reflux state to obtain 7-diethylamino-4-aldehyde coumarin (a compound shown in a formula III);
reacting 7-diethylamino-4-aldehyde coumarin with a reducing agent in a suitable solvent to obtain 7-diethylamino-4-hydroxymethyl coumarin (a compound shown in formula IV, which is called CM-OH by the name below);
in a proper solvent, the carboxylic acid perfume and the condensing agent are stirred and mixed, and then 7-diethylamino-4-hydroxymethyl coumarin is added for reaction to obtain the 7-diethylamino-4-hydroxymethyl coumarin derivative (the compound shown in the formula I).
The suitable solvent is at least one of toluene, dichloromethane, methanol, ethanol and acetonitrile.
The oxidant is selenium dioxide, copper sulfate and tert-butyl peroxide system, Collins reagent (CrO)32 Pyr).
The reducing agent is at least one of sodium borohydride, lithium aluminum hydride and aluminum isopropoxide.
The condensing agent is at least one of 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride (EDC. HCl), Dicyclohexylcarbodiimide (DCC) and benzotriazole-N, N, N ', N' -tetramethyluronium Hexafluorophosphate (HBTU).
The carboxylic acid perfume is at least one of citronellac acid, cinnamic acid, phenylpropionic acid and phenoxyacetic acid.
The molar ratio of the 7-diethylamino-4-methylcoumarin to the oxidant is 1 (1-2), and preferably 1: 1.5.
The molar ratio of the 7-diethylamino-4-aldehyde coumarin to the reducing agent is 1 (2-3), and preferably 1: 2.5.
The molar ratio of the 7-diethylamino-4-hydroxymethyl coumarin to the carboxylic acid perfume is 1 (1-2), and preferably 1: 1.5.
The molar ratio of the 7-diethylamino-4-hydroxymethyl coumarin to the condensing agent is 1 (1-1.5), and preferably 1: 1.17.
In a further aspect of the invention there is provided the use of said 7-diethylamino-4-hydroxymethylcoumarin derivative as a slow-release fragrance in the fragrance industry.
The invention further provides a slow-release aromatic, which contains the 7-diethylamino-4-hydroxymethyl coumarin derivative as an active component, wherein the weight percentage of the 7-diethylamino-4-hydroxymethyl coumarin derivative in the slow-release aromatic is 0.1-99%.
In a further aspect the invention provides the use of said fragrance of the slow release type as a perfume in the perfumery industry.
Due to the adoption of the technical scheme, the invention has the following advantages and beneficial effects:
the preparation method of the 7-diethylamino-4-hydroxymethyl coumarin derivative provided by the invention is simple, has fewer synthesis steps and low raw material cost, and is expected to be further widely applied to the field of slow release of perfumes.
The invention provides a 7-diethylamino-4-hydroxymethyl coumarin derivative, which takes 7-diethylamino-4-methylcoumarin as an initial raw material, and is subjected to selenium dioxide oxidation, sodium borohydride reduction and ester condensation reaction of corresponding carboxylic acid perfume molecules in sequence to obtain a target product, the compound is stable and weak in fluorescence under dark conditions when being used as a solution of a perfume latent perfume body, after illumination, a coumarin photo-protecting group can be broken to release the carboxylic acid perfume, the fluorescence of the carboxylic acid perfume is correspondingly enhanced, and the enhancement of the fluorescence and the release of the perfume molecules have a linear relationship, so that the release condition of the perfume molecules can be detected by a fluorescence method, and the method has the specific operations: the method firstly determines the fluorescence value of the solution under the condition of completely unreleased spice and completely released spice molecules, the enhancement ratio of the fluorescence value in the midway state is the release ratio of the spice molecules, the method is quicker, simpler and more convenient than the classical headspace test technology in the field of spice, and is a brand new method for detecting the release of the spice molecules.
Drawings
FIG. 1 is a graph showing an ultraviolet absorption spectrum (10) of CM-O-PA (a compound represented by the formula I-3) prepared in example 3 in a mixed solvent of methanol and water (v/v ═ 9:1) with increasing light exposure time-4mol·L-1)。
FIG. 2 is an embodimentFluorescence emission spectrum of CM-O-PA (compound represented by formula I-3) prepared in example 3 in a mixed solvent of methanol and water (v/v ═ 9:1) with increasing light exposure time (10)-4mol·L-1)。
FIG. 3 is a high performance liquid phase transition diagram (10) of CM-O-PA (compound of formula I-3) prepared in example 3 with increasing exposure time in a mixed solvent of methanol and water (v/v ═ 9:1)-4mol·L-1)。
FIG. 4 is a graph showing the linear relationship between the decomposition rate of CM-O-PA (a compound represented by the formula I-3) prepared in example 3 and the fluorescence-enhanced intensity of the compound in a mixed solvent of methanol and water (v/v ═ 9:1) with increasing light irradiation time (10)-4mol·L-1)。
Detailed Description
In order to more clearly illustrate the invention, the invention is further described below in connection with preferred embodiments. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and is not to be taken as limiting the scope of the invention.
The reagents and starting materials used in the present invention are commercially available or can be prepared according to literature procedures. Unless otherwise indicated, percentages and parts are by weight.
The room temperature in the embodiment of the invention is as follows: 25-28 ℃; the raw materials and reagents are all commercial products.
The reagents and materials used in the examples of the invention were as follows:
7-diethylamino-4-methylcoumarin, 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride (EDC. HCl), phenoxyacetic acid, etc. were purchased from Shanghai di Bai Biotech Co., Ltd (25g pack, purity > 98%), citronellac acid, etc. were purchased from Shanghai Zhongshi chemical Co., Ltd (5g pack, purity > 94%), selenium dioxide, cinnamic acid, phenylpropionic acid, etc. were purchased from Shanghai Milin Biotech Co., Ltd (25g pack, purity > 98%).
Example 1
Synthesis of CM-O-EA (Compound represented by the formula I-1)
(1) Synthesis of 7-diethylamino-4-aldehyde coumarin
In a 200mL round bottom flask, 7-diethylamino-4-methylcoumarin (CM-Me,3.45g,14.9mmol) and selenium dioxide (2.55g,23.0mmol) were dispersed in toluene (70mL), stirred under nitrogen at reflux for 48 hours, filtered after the reaction was complete, and the solvent was removed from the filtrate by rotary evaporation to give 2.89g of a tan solid in 79.2% yield.
(2) Synthesis of 7-diethylamino-4-hydroxymethyl coumarin
100mL of methanol was added to a 500mL round bottom flask, followed by addition of 7-diethylamino-4-formylcoumarin (2.89g,11.8mmol), addition of sodium borohydride (1.15g,30.4mmol), reaction at room temperature for 48 hours after completion of the addition, and then solvent was removed by rotary evaporation to give an oil which was purified by column chromatography (developing solvent dichloromethane) to give 1.49g of a tan solid in 51.0% yield.
(3) Synthesis of CM-O-EA
In a 50mL round bottom flask, citronellaic acid (EA,102mg,0.60mmol), EDC · HCl (90.0mg,0.47mmol), and acetonitrile (25mL) were added in this order, stirred for 10 minutes, added with 7-diethylamino-4-hydroxymethylcoumarin (CM-OH,100mg,0.40mmol), reacted at room temperature for 48 hours, and after completion of the reaction, the resulting yellow solid was dried and subjected to column chromatography to obtain 50.0mg of a pale yellow oily product with a yield of 31.0%.
1H NMR(400MHz,CDCl3,ppm):δ7.29(d,J＝9.0Hz,1H,phenyl-H),6.58(dd,J＝9.0Hz,1H,phenyl-H),6.49(d,J＝2.5Hz,1H,phenyl-H),6.11(s,1H,cy-alkene-H),5.22(d,J＝0.8Hz,2H,-OCH2-),5.08(t,J＝7.1Hz,1H,alkene-H),3.41(q,J＝7.1Hz,4H,-CH2CH3),2.45(dd,J＝15.0Hz,1H,-COCHH-),2.25(dd,J＝15.0Hz,1H,-COCHH-),2.02(m,3H,alkane-H),1.68(s,3H,CH＝C-CH3),1.60(s,3H,CH＝C-CH3),1.38(m,1H,alkane-H),1.28(m,1H,alkane-H),1.22(t,J＝7.0Hz,6H,CH2CH3),0.98(d,J＝6.9Hz,3H,-CH3).
13C NMR(100MHz,CDCl3,ppm):δ172.35,161.78,156.19,150.61,149.61,131.57,124.42,124.06,108.62,106.31,105.95,97.66,61.09,44.68,41.45,36.68,29.95,25.66,25.35,19.62,17.61,12.39.
HRMS-ESI(m/z):calcd for C24H34NO4:400.2488；[M+H]+；found:400.2487.
Example 2
Synthesis of CM-O-CA (Compound represented by the formula I-2)
(1) Synthesis of 7-diethylamino-4-aldehyde coumarin
In a 200mL eggplant-shaped flask, 7-diethylamino-4-methylcoumarin (CM-Me,3.45g,14.9mmol) and selenium dioxide (2.55g,23.0mmol) were dispersed in toluene (70mL), and the mixture was stirred under nitrogen for 48 hours under reflux, after completion of the reaction, the mixture was filtered, and the solvent was removed from the filtrate by rotary evaporation to obtain 2.89g of a tan solid, in 79.2% yield.
(2) Synthesis of 7-diethylamino-4-hydroxymethyl coumarin
100mL of methanol was added to a 500mL round bottom flask, followed by addition of 7-diethylamino-4-formylcoumarin (2.89g,11.8mmol), addition of sodium borohydride (1.15g,30.4mmol), reaction at room temperature for 48 hours after completion of the addition, and then solvent was removed by rotary evaporation to give an oil which was purified by column chromatography (developing solvent dichloromethane) to give 1.49g of a tan solid in 51.0% yield.
(3) Synthesis of CM-O-CA
Cinnamic acid (CA,160.2mg,1.08mmol), EDC & HCl (161.1mg,0.84mmol) and acetonitrile (25mL) were added sequentially to a 50mL round bottom flask, stirred for 10 minutes, added with 7-diethylamino-4-hydroxymethylcoumarin (CM-OH,180mg,0.72mmol), reacted at room temperature for 48 hours, and after completion of the reaction, the resulting yellow solid was dried and subjected to column chromatography to give 161mg of a pale yellow product in 58.0% yield.
1H NMR(400MHz,CDCl3,ppm):δ7.80(d,J＝16.0Hz,1H,alkene-H),7.57(m,2H,phenyl-H),7.42(m,3H,phenyl-H),7.34(d,J＝9.0Hz,1H,bz-phenyl-H),6.60(dd,J＝2.6Hz,1H,bz-phenyl-H),6.54(d,J＝16.0Hz,1H,alkene-H),6.53(d,J＝2.5Hz,1H,bz-phenyl-H),6.22(s,1H,β-alkene-H),5.36(d,J＝1.0Hz,2H,-CH2-),3.42(q,J＝7.1Hz,4H,CH2CH3),1.22(t,J＝7.1Hz,6H,CH2CH3).
13C NMR(100MHz,CDCl3,ppm):δ166.15,161.94,156.30,150.69,149.59,146.30,134.05,130.72,128.99,128.28,124.47,116.86,108.70,106.54,106.08,97.85,61.46,44.76,12.45.
HRMS-ESI(m/z):calcd for C23H24NO4:378.1705；[M+Na]+；found:378.1709.
Example 3
Synthesis of CM-O-PA (Compound represented by formula I-3)
(1) Synthesis of 7-diethylamino-4-aldehyde coumarin
In a 200mL eggplant-shaped flask, 7-diethylamino-4-methylcoumarin (CM-Me,3.45g,14.9mmol) and selenium dioxide (2.55g,23.0mmol) were dispersed in toluene (70mL), and the mixture was stirred under nitrogen for 48 hours under reflux, after completion of the reaction, the mixture was filtered, and the solvent was removed from the filtrate by rotary evaporation to obtain 2.89g of a tan solid, in 79.2% yield.
(2) Synthesis of 7-diethylamino-4-hydroxymethyl coumarin
100mL of methanol was added to a 500mL round bottom flask, followed by addition of 7-diethylamino-4-formylcoumarin (2.89g,11.8mmol), addition of sodium borohydride (1.15g,30.4mmol), reaction at room temperature for 48 hours after completion of the addition, and then solvent was removed by rotary evaporation to give an oil which was purified by column chromatography (developing solvent dichloromethane) to give 1.49g of a tan solid in 51.0% yield.
(3) Synthesis of CM-O-PA
Phenylpropionic acid (PA,90.1mg,0.60mmol), EDC & HCl (90.0mg,0.47mmol) and acetonitrile (25mL) are sequentially added into a 50mL round-bottom flask, stirred for 10 minutes, added with 7-diethylamino-4-hydroxymethylcoumarin (CM-OH,100mg,0.40mmol), reacted at room temperature for 48 hours, and after the reaction is finished, the yellow solid is dried and subjected to column chromatography separation to obtain 56.6mg of a light yellow product with the yield of 37.0%.
1H NMR(400MHz,CDCl3,ppm):δ7.31-7.20(m,6H,phenyl-H),6.55(dd,J＝9.0Hz,1H,phenyl-H),6.50(d,J＝2.5Hz,1H,phenyl-H),6.07(s,1H,alkene-H),5.19(d,J＝0.9Hz,2H,-CH2-),3.41(q,J＝7.1Hz,4H,CH2CH3),3.01(t,J＝7.6Hz,2H,-CH2CH2-),2.77(t,J＝7.7Hz,2H,-CH2CH2-),1.20(t,J＝7.1Hz,6H,CH2CH3).
13C NMR(100MHz,CDCl3,ppm):δ172.18,161.84,156.27,150.66,149.30,140.02,128.60,128.28,126.47,124.42,108.65,106.60,106.02,97.83,61.42,44.76,35.70,30.85,12.44.
HRMS-ESI(m/z):calcd for C23H26NO4:380.1862；[M+H]+；found:380.1855.
FIG. 1 is a graph showing an ultraviolet absorption spectrum (10) of CM-O-PA (a compound represented by the formula I-3) prepared in example 3 in a mixed solvent of methanol and water (v/v ═ 9:1) with increasing light exposure time-4mol·L-1). As can be seen from FIG. 1, as the illumination time increases, the absorption at 380nm decreases, and the color of the solution becomes lighter accordingly.
FIG. 2 shows fluorescence emission spectrum (10) of CM-O-PA (compound of formula I-3) prepared in example 3 in a mixed solvent of methanol and water (v/v ═ 9:1) with increasing light exposure time-4mol·L-1). As can be seen in FIG. 2, the fluorescence gradually increased with increasing illumination time and gradually approached CM-OH, indicating that the compound CM-O-PA decomposed to release CM-OH and the corresponding perfume molecules.
FIG. 3 is a high performance liquid phase transition diagram (10) of CM-O-PA (compound of formula I-3) prepared in example 3 with increasing exposure time in a mixed solvent of methanol and water (v/v ═ 9:1)-4mol·L-1). As can be seen from FIG. 3, as the light exposure time increased, the compound CM-O-PA gradually decomposed to release the corresponding CM-OH and fragranceTwo sets of peaks of material molecule PA further demonstrate that the compound CM-O-PA can be used for light-controlled release of fragrance molecules.
FIG. 4 is a graph showing the linear relationship between the decomposition rate of CM-O-PA (a compound represented by the formula I-3) prepared in example 3 and the fluorescence-enhanced intensity of the compound in a mixed solvent of methanol and water (v/v ═ 9:1) with increasing light irradiation time (10)-4mol·L-1). As can be seen from FIG. 4, the compound CM-O-PA has a linear relationship between the perfume release rate and its fluorescence enhancement factor: the linear relationship has the equation y-a + b x, the sum of the squares of the residuals is 0.01545, the correlation coefficient is 0.97706, the corrected decision coefficient is 0.93952, the intercept a-0.96105 has a standard error of 0.06206, the slope b-0.00778 has a standard error of 0.000979013.
Example 4
Synthesis of CM-O-PEA (Compound represented by formula I-4)
(1) Synthesis of 7-diethylamino-4-aldehyde coumarin
In a 200mL eggplant-shaped flask, 7-diethylamino-4-methylcoumarin (CM-Me,3.45g,14.9mmol) and selenium dioxide (2.55g,23.0mmol) were dispersed in toluene (70mL), and the mixture was stirred under nitrogen for 48 hours under reflux, after completion of the reaction, the mixture was filtered, and the solvent was removed from the filtrate by rotary evaporation to obtain 2.89g of a tan solid, in 79.2% yield.
(2) Synthesis of 7-diethylamino-4-hydroxymethyl coumarin
100mL of methanol was added to a 500mL round bottom flask, followed by addition of 7-diethylamino-4-formylcoumarin (2.89g,11.8mmol), addition of sodium borohydride (1.15g,30.4mmol), reaction at room temperature for 48 hours after completion of the addition, and then solvent was removed by rotary evaporation to give an oil which was purified by column chromatography (developing solvent dichloromethane) to give 1.49g of a tan solid in 51.0% yield.
(3) Synthesis of CM-O-PEA
Phenoxyacetic acid (PEA,91.3mg,0.60mmol), EDC & HCl (90.0mg,0.47mmol) and acetonitrile (25mL) are sequentially added into a 50mL round-bottom flask, stirred for 10 minutes, added with 7-diethylamino-4-hydroxymethylcoumarin (CM-OH,100mg,0.40mmol) and reacted at room temperature for 48 hours, and after the reaction is finished, the yellow solid is dried and subjected to column chromatography separation to obtain 44.0mg of a light yellow product with the yield of 28.0%.
1H NMR(400MHz,CDCl3,ppm):δ7.31(dd,J＝8.6Hz,2H,phenyl-H),7.24(d,J＝9.1Hz,1H,bz-phenyl-H),7.01(d,J＝7.4Hz,1H,phenyl-H),6.93(d,J＝8.8Hz,2H,phenyl-H),6.54(dd,J＝8.9Hz,1H,bz-phenyl-H),6.50(d,J＝2.5Hz,1H,phenyl-H),6.10(s,1H,alkene-H),5.33(d,J＝0.9Hz,2H,-CH2-),4.77(s,2H,-COCH2-),3.41(q,J＝7.1Hz,4H,CH2CH3),1.21(t,J＝7.1Hz,6H,CH2CH3).
13C NMR(100MHz,CDCl3,ppm):δ168.46,161.68,157.58,156.31,150.74,148.49,129.69,124.40,122.03,114.63,108.70,106.89,105.83,97.84,65.17,62.06,44.77,12.43.
HRMS-ESI(m/z):calcd for C22H24NO5:382.1654；[M+H]+；found:382.1654.
The foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are given by way of illustration of the principles of the present invention, and that various changes and modifications may be made without departing from the spirit and scope of the invention as defined by the appended claims. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (7)
1. A7-diethylamino-4-hydroxymethylcoumarin derivative which is one of the following compounds:
2. a sustained-release aromatic agent comprising the 7-diethylamino-4-hydroxymethylcoumarin derivative according to claim 1;
wherein, the weight percentage content of the 7-diethylamino-4-hydroxymethyl coumarin derivative is 0.1-99.0%.
3. A process for the preparation of a 7-diethylamino-4-hydroxymethylcoumarin derivative as claimed in claim 1, characterized in that it comprises the following steps:
in a proper solvent, reacting 7-diethylamino-4-methylcoumarin with an oxidant in a reflux state to obtain 7-diethylamino-4-aldehyde coumarin;
in a proper solvent, reacting 7-diethylamino-4-aldehyde coumarin with a reducing agent to obtain 7-diethylamino-4-hydroxymethyl coumarin;
in a proper solvent, stirring and mixing corresponding carboxylic acid perfume and a condensing agent, and then adding 7-diethylamino-4-hydroxymethyl coumarin for reaction to obtain a target product;
wherein the suitable solvent is selected from: at least one of toluene, dichloromethane, methanol, ethanol or acetonitrile;
the oxidant is selected from: at least one of selenium dioxide, copper sulfate, and t-butyl peroxide systems or Collins reagents;
the reducing agent is selected from: at least one of sodium borohydride, lithium aluminum hydride or aluminum isopropoxide;
the condensing agent is selected from: at least one of 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride, dicyclohexylcarbodiimide or benzotriazole-N, N, N ', N' -tetramethylurea hexafluorophosphate.
4. The method according to claim 3, wherein the molar ratio of the 7-diethylamino-4-methylcoumarin to the oxidizing agent is 1 (1-2), and the molar ratio of the 7-diethylamino-4-formylcoumarin to the reducing agent is 1 (2-3).
5. The method according to claim 3, wherein the molar ratio of the 7-diethylamino-4-hydroxymethylcoumarin to the carboxylic acid-based fragrance is 1 (1-2), and the molar ratio of the 7-diethylamino-4-hydroxymethylcoumarin to the condensing agent is 1 (1-1.5).
6. The method of claim 3, wherein the carboxylic acid based flavorant is selected from the group consisting of: at least one of citronellac acid, cinnamic acid, phenylpropionic acid or phenoxyacetic acid.
7. Use of 7-diethylamino-4-hydroxymethylcoumarin derivatives as defined in claim 1 as slow-release fragrances in the fragrance industry.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810437558.4A CN108456188B (en) | 2018-05-09 | 2018-05-09 | 7-diethylamino-4-hydroxymethyl coumarin derivative, preparation method and application thereof as nano fragrance precursor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810437558.4A CN108456188B (en) | 2018-05-09 | 2018-05-09 | 7-diethylamino-4-hydroxymethyl coumarin derivative, preparation method and application thereof as nano fragrance precursor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108456188A CN108456188A (en) | 2018-08-28 |
| CN108456188B true CN108456188B (en) | 2021-09-24 |
Family
ID=63215126
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810437558.4A Active CN108456188B (en) | 2018-05-09 | 2018-05-09 | 7-diethylamino-4-hydroxymethyl coumarin derivative, preparation method and application thereof as nano fragrance precursor |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108456188B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109503539A (en) * | 2018-12-11 | 2019-03-22 | 上海万香日化有限公司 | A kind of substitution octahydrocoumarin and preparation method thereof |
| CN111440136A (en) * | 2020-03-17 | 2020-07-24 | 北京化工大学 | Polymer with carbon dioxide/photodimerization dual response and preparation method thereof |
| CN111303101B (en) * | 2020-04-09 | 2022-06-10 | 东莞波顿香料有限公司 | Citronellyl ester compound, preparation method thereof and spice |
| CN111919843A (en) * | 2020-08-13 | 2020-11-13 | 贵州大学 | Photoresponsive chitosan-based nano pesticide and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101258140A (en) * | 2005-04-19 | 2008-09-03 | 佛莱克特瑞尔公司 | Benzo (B) cycloprop (D) pyran-2-(1H)-one derivatives |
-
2018
- 2018-05-09 CN CN201810437558.4A patent/CN108456188B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101258140A (en) * | 2005-04-19 | 2008-09-03 | 佛莱克特瑞尔公司 | Benzo (B) cycloprop (D) pyran-2-(1H)-one derivatives |
Non-Patent Citations (3)
| Title |
|---|
| Exclusive photorelease of signalling lipids at the plasma membrane;Andre Nadler et al.;《Nature Communications》;20151221;第6卷;1-10 * |
| Melding Caged Compounds with Supramolecular Containers:Photogeneration and Miscreant Behavior of the Coumarylmethyl Carbocation;Nareshbabu Kamatham et al.;《Org. Lett.》;20170620;第19卷;3588-3591 * |
| Studies on Stable Diazoalkanes as Potential Fluorogenic Reagents I 7-Substituted 4-Diazomethylcoumarins;Keiichi Ito et al.;《Chem. Pharm. Bull.》;19831231;第31卷(第9期);3014-3023 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108456188A (en) | 2018-08-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108456188B (en) | 7-diethylamino-4-hydroxymethyl coumarin derivative, preparation method and application thereof as nano fragrance precursor | |
| Jaratjaroonphong et al. | Green synthesis and anti-inflammatory studies of a series of 1, 1-bis (heteroaryl) alkane derivatives | |
| Reddy et al. | Modification of photochemistry by cyclodextrin complexation. Competitive Norrish type I and type II reactions of benzoin alkyl ethers | |
| TW201002666A (en) | Production of ethylenically unsaturated acids or esters thereof | |
| CN112010817A (en) | Method for preparing tetrazine compound and application thereof | |
| CN109970755B (en) | Synthesis of substituted salicylaldehyde derivatives | |
| EA007108B1 (en) | New process for the industrial synthesis of tetraesters of 5-[bis(carboxymethyl)amino]-3carboxymethyl-4-cyano-2-thiophenecarboxylic acid, and application to the synthesis of vivalent salts of ranelic acid and their hydrates | |
| Xu et al. | Selective aerobic oxidation of sulfides to sulfoxides catalyzed by coenzyme NAD+ models | |
| Saravanan et al. | Tetraethylammonium tetraselenotungstate: a new and efficient selenium transfer reagent for the chemoselective synthesis of functionalised diselenides | |
| CN113061077B (en) | Alpha, alpha-dideuteroalcohol compounds, deuterated drugs and preparation method thereof | |
| Zhang et al. | Study of the Paternò–Büchi type photolabile protecting group and application to various acids | |
| CN110156789B (en) | Synthetic method of azacyclo-quinazoline compound | |
| MaGee et al. | Direct furan formation by treatment of alkynyl ketones with strong potassium bases | |
| Braga et al. | One‐Pot Indium Iodide Mediated Synthesis of Chiral β‐Seleno Amides and Selenocysteine Derivatives by Ring‐Opening Reaction of 2‐Oxazolines | |
| CN108264642B (en) | 2-carbonyl acetate-based nano-aroma precursor and application thereof | |
| CN113173909A (en) | Selenium/tellurium-containing heterocyclic compound and preparation method and conversion method thereof | |
| CN108658803B (en) | Synthesis method of N, N-dialkyl diphenyl propionamide | |
| Sirinintasak et al. | Short-step syntheses and complexation properties of Z, Z-tribenzodidehydro-and all-Z-tribenzo [12] annulenes | |
| CN106749315B (en) | 8- hexyl-thieno [3 ', 2 ':3,4] benzo [1,2-c] carbazole compound and its synthetic method | |
| CN111960975A (en) | Allyl thioether compound and preparation method thereof | |
| CN110590617B (en) | Method for preparing sulfone by catalytic oxidation of thioether | |
| CN113024431B (en) | Photocatalytic synthesis method of (E) -1, 2-diseleno cyanoalkene compound | |
| CN117843536A (en) | Preparation method of diphenyl sulfone derivative | |
| RU2301796C1 (en) | Method for preparing 3-halogen-1-(ethoxycarbonyl)-alkyladamantanes | |
| CN113429272A (en) | Aryl aldehyde ketone and synthetic method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |