CN110845357B - Quaternary ammonium salt type hydrazide compound, quaternary ammonium salt type hydrazone compound prepared from same and application of quaternary ammonium salt type hydrazone compound - Google Patents
Quaternary ammonium salt type hydrazide compound, quaternary ammonium salt type hydrazone compound prepared from same and application of quaternary ammonium salt type hydrazone compound Download PDFInfo
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- C07C243/24—Hydrazines having nitrogen atoms of hydrazine groups acylated by carboxylic acids
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Abstract
The invention discloses a quaternary ammonium salt type hydrazide compound which has the following general formula:
the invention also discloses a quaternary ammonium salt type hydrazone compound prepared from the quaternary ammonium salt type hydrazide compound, which has a structure shown in the formula I:
the definition of each substituent group in the formula is shown in the specification in detail. The quaternary ammonium salt type hydrazone compound has good water solubility, and after the quaternary ammonium salt type hydrazone compound releases perfume aldehyde ketone under an acidic condition, the quaternary ammonium salt type hydrazide compound remained in a solution system has excellent surface activity, and is a good surfactant.
Description
Technical Field
The invention belongs to the technical field of preparation of novel quaternary ammonium salt hydrazone compounds, and particularly relates to a quaternary ammonium salt type hydrazide compound, a quaternary ammonium salt type hydrazone compound prepared from the quaternary ammonium salt type hydrazide compound and application of the quaternary ammonium salt type hydrazone compound.
Background
The perfume, as one of the organic volatile compounds, is paid attention to by people due to its unique properties, not only has the advantages of improving environmental smell, making people relaxed and happy, but also has various psychophysiological medical health-care functions of sterilization, refreshing and restoring consciousness and the like, and is popular with people from ancient times to present. The perfume and essence can be used as a functional aromatic product, is widely applied to daily necessities (perfume, food additive, textile, leather, paper, cosmetics, washing products, tobacco, medicine and the like), and is closely related to national economy and people's life. Most of the perfume materials are volatile small molecular compounds, so that the perfume materials cannot keep long-term fragrance, and in order to solve the problem, the research of latent perfume bodies is concerned by people.
Latent fragrances are non-volatile and odourless compounds that selectively undergo chemical bond cleavage under specific conditions and release one or more fragrance active molecules simultaneously. The conditions under which the chemical bond cleavage occurs are generally mild and mainly include temperature changes, light irradiation, ubiquitous oxygen, changes in humidity (including changes in acidic pH), catalysis by different enzymes, fermentation by microorganisms, and the like. Currently, latent aromatic molecules of schiff base type have been the focus of research due to the properties of simple synthesis and mild hydrolysis conditions, but the schiff base is too unstable and even difficult to separate and purify, so that the schiff base is limited in utilization. The hydrazone compound is similar to Schiff base in property, can release aldehyde ketone compound under acidic condition, but has better stability than Schiff base, and can replace Schiff base type latent perfume molecules under certain environment. Trimethylaminoacethydrazide chloride, which is a Girad-T reagent, can also react with aldone to form a hydrazone compound soluble in water, and then the aldone compound is liberated under acidic conditions by water, which is a compound usually used for separating and purifying aldone. The existing latent perfume body has poor water solubility and most of the compounds remained after the perfume molecules are released are useless, so that the synthesis of the latent perfume compound which has good water solubility and the same function as the substances remained in a solution system after the perfume molecules are released becomes a technical problem to be solved.
Disclosure of Invention
It is a first object of the present invention to provide a hydrazide compound of the quaternary ammonium salt type.
The second purpose of the invention is to provide a preparation method of the hydrazide compound in the quaternary ammonium salt type.
The third purpose of the invention is to provide a quaternary ammonium salt type hydrazone compound prepared by the quaternary ammonium salt type hydrazide compound and an application of the quaternary ammonium salt type hydrazone compound in slow release of perfume.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
in a first aspect, the present invention provides a hydrazide compound of the quaternary ammonium salt type, having the following general formula:
R 1 、R 2 、R 3 each independently selected from hydrogen, substituted or unsubstituted C 1 -C 20 An alkyl group; r 1 、R 2 、R 3 Not hydrogen at the same time;
x is halogen (F, Cl, Br or I).
More preferably, the quaternary ammonium salt type hydrazide compound is one of the following structures:
the second aspect of the present invention provides a method for preparing the hydrazide compound of quaternary ammonium salt type, comprising the steps of:
mixing N, N-dimethyl glycine ethyl ester and alkyl halide in a molar ratio of 1 (1.01-2) (preferably 1:1.1) for reaction at 20-60 ℃ for 1-48 h to obtain a quaternary ammonium salt type ester compound;
dissolving hydrazine hydrate in a solvent, adding the mixture of the obtained quaternary ammonium salt type ester compound and the solvent, wherein the molar ratio of the hydrazine hydrate to the quaternary ammonium salt type ester compound is (5-15): 1 (preferably 10:1), and reacting to obtain the quaternary ammonium salt type hydrazide compound.
The alkyl halide is bromohexadecane, bromotetradecane, bromododecane, bromodecane, bromooctane, bromoheptane, bromobutane, 1,1,1,2,2,3,3,4,4,5,5,6,6,7,7,8, 8-heptadecafluoro-10-iodoheptane.
The solvent is ethanol, methanol or toluene.
The third aspect of the present invention provides a quaternary ammonium hydrazone compound having a structure represented by formula I:
in the formula I, the compound is shown in the specification,
R 1 、R 2 、R 3 each independently selected from hydrogen, C 1 -C 20 An alkyl group; r 1 、R 2 、R 3 Not hydrogen at the same time;
R 4 selected from hydrogen, C 1 -C 20 An alkyl group;
R 5 selected from hydrogen, substituted or unsubstituted aryl, C 1 -C 20 Alkenyl-substituted aryl;
R 4 and R 5 Not hydrogen at the same time;
R 6 is hydrogen, C 1 -C 20 An alkyl group;
x is halogen (F, Cl, Br or I).
More preferably, in said formula I,
R 1 、R 2 、R 3 each independently selected from hydrogen, C 7 -C 16 An alkyl group; r 1 、R 2 、R 3 Is not hydrogen at the same time;
R 4 selected from hydrogen, methyl;
R 5 selected from hydrogen, substituted or unsubstituted phenyl, substituted or unsubstituted benzoheterocycle, C 1 -C 20 Alkenyl radicals being taken fromA substituted phenyl group;
R 4 and R 5 Not hydrogen at the same time;
R 6 is hydrogen or methyl;
x is Cl or Br.
More preferably, in said formula I,
R 1 、R 2 、R 3 each independently selected from hydrogen, C 12 H 25 ；R 1 、R 2 、R 3 Is not hydrogen at the same time;
R 4 selected from hydrogen, C 1 -C 5 An alkyl group;
R 5 selected from hydrogen,
R 4 And R 5 Is not hydrogen at the same time;
R 6 is hydrogen or methyl;
and X is Br.
Most preferably, the quaternary ammonium hydrazone compound is one of the following structures:
the fourth aspect of the present invention provides a method for preparing the quaternary ammonium salt hydrazone compound, comprising the steps of:
dissolving a quaternary ammonium salt type hydrazide compound and aldehyde or ketone perfume in a molar ratio of 1 (1.1-2) (preferably 1:1.5) in a solvent, and performing reflux reaction to obtain the quaternary ammonium salt type hydrazone compound.
The solvent is ethanol, methanol or toluene.
The aldehyde or ketone perfume is cinnamaldehyde, heliotropin, 4-phenyl-2-butanone, cyclamenal, beta-ionone, citronellal, benzaldehyde, anisaldehyde, phenylacetaldehyde, vanillin, lilial, ligustral, menthone, cyclopentadecanone, acetophenone, p-methylacetophenone, p-methoxyacetophenone, tonalid, damascenone, amylcyclopentanone, and apione.
The fifth aspect of the invention provides an application of the quaternary ammonium salt hydrazone compound in slow release of perfume.
A sixth aspect of the invention provides the use as a slow release perfume agent.
Due to the adoption of the technical scheme, the invention has the following advantages and beneficial effects:
the quaternary ammonium salt hydrazone compound with a long carbon chain prepared by the invention has excellent water solubility and good surface activity, and is a multifunctional surfactant with a slow-release fragrance effect. The synthesis method used by the invention has simple steps and mild reaction conditions. The synthesized quaternary ammonium salt type hydrazide compound can react with aldehyde ketone in an aqueous solution, has good surface activity, and not only has the capability of reducing the surface tension of water but also can keep the fragrance in a washing product for a longer time if the compound is matched with some washing products with weak acidity for use, so that the compound has certain market application prospect.
Drawings
FIG. 1 is a schematic of the surface tension-concentration curve of a hydrazide compound of the quaternary ammonium salt type.
FIG. 2 is a schematic representation of the equilibrium process of UV-Vis spectroscopy for the hydrolysis and formation of a hydrazone compound in a citric acid buffer at pH 4.5.
FIG. 3 is a schematic diagram of the equilibrium process of UV-Vis spectrum test for the hydrolysis and formation of hydrazone compound in phosphoric acid buffer solution with pH of 2.5.
FIG. 4 is a graphical representation of the time-concentration profile of cinnamaldehyde release from a quaternary ammonium hydrazone compound A and a neat fragrance material.
FIG. 5 is a graphical representation of the time-concentration profile of heliotropin release from a quat type hydrazone compound B and a pure fragrance material.
FIG. 6 is a graph showing the time-concentration profile of 4-phenyl-2-butanone release from a quaternary ammonium hydrazone compound C and a pure perfume material.
FIG. 7 is a graphical representation of the time-concentration profile of the release of cyclamen from a quaternary hydrazone compound D and a pure fragrance material.
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.
Example 1
The preparation method of the quaternary ammonium salt hydrazone compound comprises the following steps:
(1) 0.65g (5mmol) of ethyl N, N-dimethylglycinate and 1.37g (5.5mmol) of bromododecane were added to the reaction tube, and the mixture was reacted at 40 ℃ for 24 hours without adding a solvent. And (3) adding anhydrous ether into the reaction tube after the reaction is finished, washing, standing to obtain an oily liquid at the lower layer, separating the oily liquid, continuously washing twice with ether, and recrystallizing with ether to obtain the white quaternary ammonium salt type ester compound, wherein the yield is 70%.
(2) 0.25g (5mmol) of hydrazine hydrate is weighed and dissolved in 15mL of ethanol, 0.2g (0.5mmol) of the quaternary ammonium salt type ester compound obtained in the previous step is dissolved in 10mL of ethanol, and then slowly added into an ethanol solution of hydrazine hydrate for reaction for 6h at room temperature. And (3) after the reaction is finished, decompressing, removing part of ethanol solvent by spinning, putting the mixture into a refrigerator for cooling overnight, separating out white solid, performing suction filtration, and washing the white solid with glacial ethanol to obtain the quaternary ammonium salt type hydrazide compound (the structure is shown in a formula 3a), wherein the yield is 83%.
1 H NMR(400MHz,CDCl 3 )δ4.65(s,2H),3.65(dd,J＝10.2,6.7Hz,2H),3.44(s,6H),1.79(s,2H),1.31(d,J＝40.6Hz,20H),0.88(t,J＝6.8Hz,3H).
(3) To a round-bottomed flask was added 0.384g (0.8mmol) of the synthesized hydrazide compound of quaternary ammonium salt type, 0.158g (1.2mmol) of cinnamaldehyde was added, and finally 15mL of ethanol was added as a solvent to conduct a reflux reaction for 4 hours. After the reaction is finished, cooling to room temperature, and performing column chromatography separation by using petroleum ether/ethyl acetate as an eluent to obtain a light yellow target product (the structure is shown as a formula A), wherein the yield is 78%.
1 H NMR(400MHz,CDCl 3 )δ12.61(s,1H),8.35(d,J＝8.4Hz,1H),7.47–7.42(m,2H),7.35(m,3H),7.00(d,J＝6.9Hz,1H),4.71(s,1H),3.68–3.59(m,2H),3.42(s,6H),2.07(s,2H),1.83(s,2H),1.31(d,J＝48.6Hz,18H),0.88(t,J＝6.9Hz,3H).
13 C NMR(100MHz,CDCl 3 )δ158.88,152.95,142.26,135.61,129.38,128.86,127.33,124.44,66.65,62.65,52.22,31.89,29.58,29.42,29.36,29.32,29.07,26.16,22.96,22.68,14.14.
HRMS(ESI-TOF)m/z:[M-Br] + Calcd for C 25 H 42 N 3 O 400.3328；Found 400.3322.
Example 2
The preparation method of the quaternary ammonium salt hydrazone compound comprises the following steps:
the same conditions as those in example 1 were repeated except that cinnamaldehyde in step (3) of example 1 was changed to helional, to obtain a compound represented by formula B.
1 H NMR(400MHz,CDCl 3 )δ12.29(s,1H),7.86(d,J＝6.2Hz,1H),6.64(m,3H),5.92(s,2H),4.65(d,J＝3.9Hz,2H),3.69–3.56(m,2H),3.40(s,6H),2.88(dd,J＝13.6,5.8Hz,1H),2.79–2.64(m,1H),2.49(dd,J＝13.6,8.9Hz,1H),2.09(s,1H),1.82(s,2H),1.44–1.19(m,18H),1.05(d,J＝6.8Hz,3H),0.88(t,J＝6.8Hz,3H).
13 C NMR(100MHz,CDCl 3 )δ159.34,158.70,147.54,145.91,132.93,122.17,109.48,108.15,100.79,66.64,62.49,52.18,39.89,39.02,31.88,29.57,29.55,29.40,29.33,29.30,29.05,26.13,22.93,22.67,16.79,14.12.
HRMS(ESI-TOF)m/z:[M-Br] + Calcd for C 27 H 46 N 3 O 3 460.3539；Found 460.3544.
Example 3
The preparation method of the quaternary ammonium salt hydrazone compound comprises the following steps:
the same conditions as described in example 1 were repeated except that cinnamaldehyde was changed to 4-phenyl-2-butanone in the step (3) of example 1, to obtain a compound represented by the formula C.
1 H NMR(400MHz,CDCl 3 )δ7.29(d,J＝6.8Hz,2H),7.19(t,J＝7.9Hz,3H),4.89(s,2H),3.79–3.57(m,2H),3.39(d,J＝16.5Hz,6H),2.89(dd,J＝11.7,5.0Hz,3H),2.66(dd,J＝10.1,6.5Hz,2H),2.25(d,J＝1.7Hz,2H),1.80(s,2H),1.45–1.16(m,18H),0.88(t,J＝6.6Hz,3H).
13 C NMR(100MHz,CDCl 3 )δ208.06,162.75,159.65,140.98,128.86,128.48,128.34,126.11,66.43,62.47,51.93,45.16,41.09,32.74,31.89,30.10,29.71,29.57,29.56,29.41,29.31,29.08,26.14,22.92,22.68,18.97,14.13.
HRMS(ESI-TOF)m/z:[M-Br] + Calcd for C 23 H 46 N 3 O 416.3641；Found 416.3641.
Example 4
The preparation method of the quaternary ammonium salt hydrazone compound comprises the following steps:
the compound represented by the formula D was obtained under the same conditions as described in example 1 except that cinnamaldehyde was changed to galbane in step (3) of example 1.
1 H NMR(400MHz,CDCl 3 )δ7.88(d,J＝6.2Hz,1H),7.11(dd,J＝22.5,8.1Hz,4H),4.65(d,J＝3.1Hz,2H),3.72–3.57(m,2H),3.40(s,6H),2.87(dt,J＝17.7,6.9Hz,1H),2.76(m,1H),2.51(dd,J＝13.5,9.2Hz,1H),1.81(s,2H),1.45–1.16(m,25H),1.05(d,J＝6.8Hz,3H),0.88(t,J＝6.8Hz,3H).
13 C NMR(100MHz,CDCl 3 )δ159.62,158.75,146.68,136.43,129.12,126.40,66.57,62.47,52.20,39.71,38.84,33.68,31.89,29.57,29.56,29.41,29.06,26.14,24.05,22.94,22.67,16.79,14.13.
HRMS(ESI-TOF)m/z:[M-Br] + Calcd for C 29 H 52 N 3 O 458.4110；Found 458.4100.
Example 5
Measurement of surface tension of hydrazide compound of quaternary ammonium salt type:
quaternary ammonium salt type hydrazide compounds with carbon chain lengths of 7 (structural formula 1 a), 10 (structural formula 2 a), 12 (structural formula 3a), 14 (structural formula 4 a), 16 (structural formula 5 a) and long fluorine chains (structural formula 6 a) were synthesized according to the methods of steps (1) and (2) in example 1, and all of these compounds have good solubility in water. In the process of testing the surface tension, 40mL of water is taken as a reference, a prepared sample solution to be tested with the concentration of 0.01mol/L is gradually added, and finally, logC with the added sample concentration is taken as an abscissa and the surface tension value of the water is taken as an ordinate to carry out plotting so as to obtain a surface tension-concentration curve.
1 H NMR(400MHz,CDCl 3 )δ4.64(s,2H),3.70–3.60(m,2H),3.45(s,6H),1.80(s,2H),1.45–1.23(m,8H),0.89(t,J＝6.9Hz,3H).
1 H NMR(400MHz,CDCl 3 )δ4.62(s,2H),3.74–3.57(m,2H),3.45(d,J＝14.2Hz,6H),1.79(s,2H),1.42–1.15(m,14H),0.88(t,J＝6.8Hz,3H).
1 H NMR(400MHz,CDCl 3 )δ4.65(s,2H),3.65(dd,J＝10.2,6.7Hz,2H),3.44(s,6H),1.79(s,2H),1.31(d,J＝40.6Hz,20H),0.88(t,J＝6.8Hz,3H).
1 H NMR(400MHz,CDCl 3 )δ4.63(s,2H),3.73–3.58(m,2H),3.43(s,6H),1.79(s,2H),1.31(d,J＝40.8Hz,22H),0.88(t,J＝6.8Hz,3H).
1 H NMR(400MHz,CDCl 3 )δ4.64(s,2H),3.70–3.58(m,2H),3.43(s,6H),1.79(s,2H),1.43–1.12(m,26H),0.88(t,J＝6.8Hz,3H).
1 H NMR(400MHz,CDCl 3 )δ3.98(s,2H),3.3((s,6H),3.22(t,J＝7.2Hz,2H),2.10–1.92(m,2H). 13 C NMR(100MHz,CDCl 3 )δ171.32,118.25,112.76,109.57,71,78,51.65,50,43,19,23.HRMS(ESI-TOF)m/z:[M-I] + Calcd for C 14 H 15 F 17 N 3 O 569.0944；Found 569.0941.
The test result is shown in fig. 1, fig. 1 is a surface tension-concentration curve diagram of the quaternary ammonium salt type hydrazide compound, and it can be seen from the graph that, when the carbon chain length is 7, the surface tension of water after the sample to be tested is added is not changed much, which indicates that the compound has no surface activity. The addition of other compounds was effective in reducing the surface tension of water, and it can be seen that the surface activity gradually increased as the carbon chain length increased from 7 to 12, but the ability to reduce the surface tension of water gradually decreased as the carbon chain length continued to increase at 14 and 16. When the carbon chain length is 12, the surface tension of water can be reduced to about 18.68mN/m, which indicates that the surfactant is a good surfactant. Meanwhile, a long-fluorine-chain quaternary ammonium salt type hydrazide compound is synthesized, which can reduce the surface tension of water to about 31.53mN/m, which shows that the compound also has certain surface activity, but the effect is general. From the surface tension test, it was found that the hydrazide compound had the best surface activity when the carbon chain length was 12. The hydrazone compound is used as a matrix to react with perfume aldehyde ketone to generate a corresponding hydrazone compound, and then the performance of the hydrazone compound for releasing the perfume is tested.
Example 6
Hydrolysis and formation of quaternary hydrazones test the kinetic equilibrium of quaternary hydrazones:
in order to research the condition property of quaternary ammonium hydrazone compounds for releasing perfume through hydrolysis and the hydrolysis rate of the quaternary ammonium hydrazone compounds in different acidic aqueous solutions, an ultraviolet-visible spectrophotometer is utilized to hydrolyze the quaternary ammonium hydrazone compounds and form dynamic balance for testing, and the ultraviolet-visible spectrophotometer can not only test the maximum absorption wavelength of the compounds so as to determine the structures of the compounds, but also measure the dynamic spectrum of a sample solution in reaction for multiple times of repetition and track the changes of the structures and the concentrations of the compounds in the reaction process in real time. Selecting hydrazide compound with carbon length of 12 (structure shown as formula 3a) and vanillin, and hydrazone compound synthesized from them as raw material, and performing kinetic analysis.
Preparing buffer solutions with different acidity:
preparation of citric acid buffer solution with pH 4.5: 0.65g of sodium hydroxide, 0.62g of sodium chloride and 2.58g of citric acid are sequentially weighed and dissolved in 160.02g of deionized water, 31.45g of absolute ethyl alcohol is added to prepare a solution, 10mL of the prepared solution is taken, 2mL of absolute ethyl alcohol is added to prepare a citric acid buffer solution with the volume ratio of water to ethyl alcohol being 2:1 and the pH value being 4.5.
preparation of phosphate buffer solution with pH 2.5: 1.97g of phosphoric acid, 1.37g of monopotassium phosphate and 0.6g of sodium chloride are respectively weighed and dissolved in 160.01g of water, 31.45g of absolute ethyl alcohol is added to prepare a solution, 10mL of the prepared solution is taken, 2mL of absolute ethyl alcohol is added to prepare a phosphoric acid buffer solution with the volume ratio of water to ethyl alcohol being 2:1 and the pH value being 2.5.
Testing of the ultraviolet-visible spectrum: the cuvette used for the test was a 3mL quartz cuvette, from which 0.2mL of hydrazide compound and 0.2mL of vanillin (both substances were made up to 2.0X 10) -4 mol/L ethanol solution) was added to the cuvette, and 1.6mL of a citric acid buffer solution having a pH of 4.5 was added to the cuvette so as to prepare a solution having a water-ethanol volume ratio of 2:1 and a concentration of 1.7X 10 -5 mol/L solution. The test is started after two minutes from the prepared solution, the test time interval is 30min, and the test is mainly carried out on the formation process of the hydrazone compound when the pH value is 4.5. The amount of hydrazone compound used in the cuvette was 0.4mL (prepared at 1.0X 10) -4 mol/L ethanol solution) was added with 1.6mL of citric acid buffer solution of pH 4.5 for the same 30min interval. Finally, the citric acid buffer solution with the pH value of 4.5 was replaced with a phosphoric acid buffer solution with the pH value of 2.5 to perform the above two tests, wherein the time interval between the tests was 5min, and the obtained UV-visible spectra are shown in FIGS. 2 and 3, FIG. 2 is a schematic diagram of the equilibrium process of hydrolysis and formation of the UV-visible spectra test hydrazone compound in the citric acid buffer solution with the pH value of 4.5, and FIG. 3 is a schematic diagram of the equilibrium process of hydrolysis and formation of the UV-visible spectra test hydrazone compound in the phosphoric acid buffer solution with the pH value of 2.5.
As shown in FIG. 2, the lower curve represents the process of forming hydrazone compound from mixture of hydrazide compound and vanillin in acidic aqueous solution, the absorbance gradually increases with time, and the smaller and smaller amplitude of the increase in absorbance can be seen in the figure, which indicates that the reaction proceeds relatively fast at the beginning and gradually slows down to reach the equilibrium; the upper curve represents the hydrolysis of the hydrazone compound, and the absorbance gradually decreases with time and eventually reaches equilibrium. The reaction of the hydrazide compound and vanillin in the mixed acidic aqueous solution of water and ethanol is visually reflected in the figure.
As shown in FIG. 3, the dynamic equilibrium process of the hydrolysis and formation of hydrazone compound in the aqueous solution with strong acidity is tested, and it can be seen from the figure that the hydrazone compound is hydrolyzed and formed in the aqueous solution with strong acidity at a high speed and is easily in equilibrium. As can be seen from a comparison of FIGS. 2 and 3, the hydrazone compound is more easily hydrolyzed under the more acidic condition, and the reaction between the hydrazide compound and vanillin proceeds more rapidly as the acidity increases.
Two conclusions can be drawn from the above; the synthesized novel quaternary ammonium salt type hydrazide compound (compound 3a) can perform a balance reaction with vanillin in an acidic aqueous solution, which has a certain positive significance for the slow release application of perfume substances, and meanwhile, the synthesized hydrazone compound is slower in the rate of aldehyde ketone release through hydrolysis under the condition of weaker acidity, which provides a theoretical basis for the slow release effect of the hydrazone compound to be tested.
Example 7
And (3) detecting aldehyde ketone perfume substances released by quaternary ammonium salt hydrazone compounds on the surface of cotton cloth:
the test of the latent aromatic molecule release perfume substance on the surface of the cotton cloth is a conventional test method, can simulate the environment state of the latent aromatic compound in practical application, and is beneficial to evaluating the release performance of the latent aromatic. In the experiment, the concentration of the hydrazone compound releasing the perfume substances on the surface of the cotton cloth and the concentration of the aroma substances of equimolar pure perfume molecules releasing on the surface of the cotton cloth are detected by using a solid phase microextraction-gas chromatography method, and the comparison of the two sets of concentration data shows that the hydrazone compound has the effect of controlling and delaying the release of the perfume substances.
In a plurality of washing products, perfume substances are mixed with surfactants for use, wherein a cationic surfactant is used as a fabric softener, the fabric softener can be well attached to clothes, and can promote some nonpolar organic small molecules such as perfume substances to be well adsorbed on cotton clothes, so that triethanolamine fatty acid ester quaternary ammonium salt is added as the fabric softener in the experimental process, and the fabric softener is a novel fabric softener and has the characteristics of excellent softness, antistatic property, rewetting property, biodegradability and the like.
The specific test method comprises the following steps: firstly, adding 1.8g triethanolamine fatty acid ester quaternary ammonium salt into 50mL deionized water, stirring uniformly, adding 5mL or 0.01mol cinnamyl aldehyde, heliotropin, 4-phenyl-2-butanone or conyzal dissolved with 0.01mol quaternary ammonium salt hydrazone compound (A, B, C, D), adding citric acid to adjust the pH value of the solution to 3.1, and standing for 12 hours to achieve dynamic balance. Then adding deionized water to adjust pH of the solution to 4.0-4.2, soaking a piece of cotton cloth of 12 × 12cm in the solution, mechanically stirring for 10min, standing for 5min to adsorb hydrazone compound and perfume substance on the cotton cloth, wringing out with hand, and naturally drying overnight. Uniformly spraying 2mL of acidic aqueous solution with the pH value of 4.5 (0.65 g of sodium hydroxide, 0.62g of sodium chloride and 2.58g of citric acid are dissolved in 160.02g of deionized water, then 31.45g of ethanol is added to prepare a solution, 10mL of the prepared solution is taken, 2mL of absolute ethanol is added to prepare a citric acid buffer solution with the volume ratio of the absolute ethanol to the water to the ethanol of 2:1 and the pH value of 4.5) on cotton cloth, cutting the cotton cloth into fine fragments, putting the fragments into a 20mL overhead bottle, adding 20 mu L of o-dichlorobenzene (100ppm) as an internal standard substance, and sealing for solid phase microextraction.
Solid phase micro-extraction operating conditions: the method comprises the steps of carrying out aging treatment on a fiber head before the fiber head is extracted by SPME (spinning jet mill), removing organic matters remained on the fiber head to prevent error interference, aging the extraction fiber head for 30min at the temperature of 250 ℃ under the protection of an injection port and inert gas of a gas chromatograph, inserting the aged extraction fiber head into a headspace part (note: the extraction head cannot be contacted with a substance to be detected, and the extraction head is prevented from being broken and polluted) in a sample bottle, extracting for 1h at the temperature of 35 ℃, taking out the extraction fiber head after extraction is finished, rapidly inserting a needle into an injection port of a gas chromatograph, safely pushing out the fiber head, carrying out thermal analysis on adsorbed aroma components, wherein the analysis time is 5min, and simultaneously starting the gas chromatograph to carry out data acquisition and analysis.
A schematic diagram of a time-concentration curve is obtained by plotting time as an abscissa and concentration of an aroma substance released as an ordinate, as shown in fig. 4-7, fig. 4 is a schematic diagram of a time-concentration curve of cinnamaldehyde released by a quaternary ammonium hydrazone compound a and a pure perfume substance, fig. 5 is a schematic diagram of a time-concentration curve of heliotropin released by a quaternary ammonium hydrazone compound B and a pure perfume substance, fig. 6 is a schematic diagram of a time-concentration curve of 4-phenyl-2-butanone released by a quaternary ammonium hydrazone compound C and a pure perfume substance, and fig. 7 is a schematic diagram of a time-concentration curve of cyclamen released by a quaternary ammonium hydrazone compound D and a pure perfume substance.
As can be seen from fig. 4 to 7, the concentration of the perfume released from all the quaternary ammonium hydrazone compounds is greater than the concentration of the pure perfume, which is mainly caused by two processes, the first process is to balance for 12 hours after the quaternary ammonium hydrazone compound is added, the quaternary ammonium hydrazone compound is partially hydrolyzed in the balancing process, a part of the perfume is volatilized, and a part of the perfume and the hydrazide reach a dynamic equilibrium state in the aqueous solution; pure fragrance materials, however, initially evaporate slowly because they are not covalently bound to other materials. The other process is a drying process in which the quaternary ammonium hydrazone compound and the perfume substance are adsorbed on the cotton cloth, and as the water is continuously evaporated in the drying process, the hydrolysis rate of the quaternary ammonium hydrazone compound is also continuously reduced, so that a small amount of the perfume substance is volatilized into the air; the pure spice substances can be volatilized all the time, the temperature of the cotton cloth can be reduced by volatilization of water under the condition that the water exists to slow down the release of the spice substances, the speed of diffusing the spice substances on the cotton cloth into the air can be further accelerated after the water is volatilized, and the volatilization concentration of the pure spice substances is always smaller than that of the spice substances released from the quaternary ammonium salt type hydrazone compounds.
Comparing fig. 4 to 7, it can be found that the concentration of the perfume substance released by the quaternary ammonium salt type hydrazone compound C is the largest, and the release concentration of the corresponding pure perfume substance 4-phenyl-2-butanone is the smallest, which is caused by the low boiling point of 4-phenyl-2-butanone, and the volatilization amount of pure perfume molecules on cotton cloth is large due to the low boiling point, so that the volatilization concentration is low during the test; and 4-phenyl-2-butanone released after the quaternary ammonium salt type hydrazone compound C is hydrolyzed can be quickly volatilized into the air, so that the concentration of the quaternary ammonium salt type hydrazone compound C in a headspace bottle is relatively high. The comparison of fig. 4-7 shows that the pure heliotropin has a higher volatile concentration than other aldehydes and ketones, mainly because heliotropin has a boiling point of 134-. Experiments show that the hydrazone compound can delay the volatilization of the perfume material by about 10 times, so that the quaternary ammonium salt type hydrazone compound prepared in the application (examples 1-4) has the conclusion of controlling and delaying the release of the perfume material.
The quaternary ammonium salt type hydrazone compound prepared by the application can be hydrolyzed in an aqueous solution to release aldehyde ketone perfume substances, and the quaternary ammonium salt type hydrazide compound remained in a solution system after hydrolysis also has good surface activity, and if the quaternary ammonium salt type hydrazone compound is matched with some washing products with weak acidity for use, the quaternary ammonium salt type hydrazone compound not only has the capability of reducing the surface tension of water, but also can enable fragrance in the washing products to be more fragrant for a longer time, so that the quaternary ammonium salt type hydrazone compound has a certain market application prospect.
Although the present invention has been described with reference to a preferred embodiment, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (5)
1. A quaternary ammonium hydrazone compound having a structure represented by formula I:
in the formula I, the compound is shown in the specification,
R 1 、R 2 、R 3 each independently selected from hydrogen, C 1 -C 20 An alkyl group; r 1 、R 2 、R 3 Not hydrogen at the same time;
R 4 selected from hydrogen, C 1 -C 20 An alkyl group;
R 5 selected from hydrogen,
R 4 And R 5 Not hydrogen at the same time;
R 6 selected from hydrogen, C 1 -C 20 An alkyl group;
x is halogen.
2. The quaternary ammonium hydrazone compound according to claim 1, wherein in formula I,
R 1 、R 2 、R 3 each independently selected from hydrogen, C 7 -C 16 An alkyl group; r 1 、R 2 、R 3 Not hydrogen at the same time;
R 4 selected from hydrogen, methyl;
R 5 selected from hydrogen,
R 4 And R 5 Not hydrogen at the same time;
R 6 selected from hydrogen, methyl;
and X is Cl or Br.
3. The quaternary ammonium hydrazone compound according to claim 2, wherein in formula I,
R 1 、R 2 、R 3 each independently selected from hydrogen, C 12 H 25 ；R 1 、R 2 、R 3 Not hydrogen at the same time;
R 4 selected from hydrogen, C 1 -C 5 An alkyl group;
R 4 and R 5 Not hydrogen at the same time;
R 6 selected from hydrogen, methyl;
and X is Br.
4. The quaternary ammonium hydrazone compound of claim 3, wherein said quaternary ammonium hydrazone compound is one of the following structures:
5. use of a quaternary hydrazone compound according to any one of claims 1 to 4 as a slow-release agent for perfume.
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Citations (3)
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|---|---|---|---|---|
| US4978670A (en) * | 1986-04-07 | 1990-12-18 | The Upjohn Company | Anthelmintic quaternaryalkyl acylhydrazones, method of use and compositions |
| AU2399500A (en) * | 1998-12-31 | 2000-07-31 | Akzo Nobel N.V. | Cationic gemini and related multiple hydrophilic/hydrophobic functional compounds and their use as surfactants |
| CN101679463A (en) * | 2007-01-09 | 2010-03-24 | 脉管生物生长有限公司 | Improved process for the preparation of oxidized phospholipids |
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| US6890920B2 (en) * | 2001-10-26 | 2005-05-10 | Pharmacia & Upjohn Company | Quaternary ammonium compounds |
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|---|---|---|---|---|
| US4978670A (en) * | 1986-04-07 | 1990-12-18 | The Upjohn Company | Anthelmintic quaternaryalkyl acylhydrazones, method of use and compositions |
| AU2399500A (en) * | 1998-12-31 | 2000-07-31 | Akzo Nobel N.V. | Cationic gemini and related multiple hydrophilic/hydrophobic functional compounds and their use as surfactants |
| CN101679463A (en) * | 2007-01-09 | 2010-03-24 | 脉管生物生长有限公司 | Improved process for the preparation of oxidized phospholipids |
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| A modified Girard derivatizing reagent for universal profiling and trace analysis of aldehydes and ketones by electrospray ionization tandem mass spectrometry;David W. Johnson;《Rapid Communications In Mass Spectrometry》;20070806;第21卷(第18期);第2926-2932页 * |
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