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

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

Quaternary ammonium salt type hydrazide compound and quaternary ammonium salt type hydrazone compound prepared therefrom and application

technical field

The invention belongs to the technical field of preparation of novel quaternary ammonium salt hydrazone compounds, and in particular relates to a quaternary ammonium salt type hydrazide compound, a quaternary ammonium salt type hydrazone compound prepared therefrom, and applications.

Background technique

As a large category of organic volatile compounds, spices have attracted people's attention due to their unique properties. Spices not only have the advantages of improving the atmosphere of the environment, making people feel refreshed and comfortable, but also have the advantages of sterilization, refreshing and other psychophysiological properties. The health care function on the device has been loved by people since ancient times. As a functional aroma product, spice and essence are widely used in daily necessities (perfume, food additives, textiles, leather, papermaking, cosmetics and detergents, tobacco, medicines, etc.), and are closely related to the national economy and people's lives. Since most of the fragrance substances are volatile and small molecular compounds, they cannot maintain long-lasting fragrance. In order to solve this problem, the research on latent fragrance bodies has attracted people's attention.

Latent fragrance bodies are non-volatile and odorless compounds, which can selectively break chemical bonds under specific conditions and release one or several fragrance active molecules at the same time. The conditions under which chemical bond cleavage occurs are generally mild, and these conditions mainly include changes in temperature, irradiation of light, ubiquitous oxygen, changes in humidity (including changes in acidic pH), as well as catalysis by different enzymes and fermentation by microorganisms Wait. The Schiff base-type latent odorant molecules have always been a research hotspot due to their simple synthesis and mild hydrolysis conditions, but their utilization is limited due to the fact that Schiff bases are too unstable and some are even difficult to separate and purify. The properties of hydrazone compounds are similar to those of Schiff bases, and they can also be hydrolyzed under acidic conditions to release aldehydes and ketones, but their stability is better than that of Schiff bases, and can replace Schiff base-type latent fragrant body molecules under certain circumstances. Trimethylaminoacetazide chloride (Girard-T reagent) can also react with aldehydes and ketones to form water-soluble hydrazone compounds, which are then hydrolyzed under acidic conditions to release aldehydes and ketones. It is usually used to separate and purify aldehydes and ketones. class of compounds. The existing latent fragrance bodies are all poorly water-soluble and the remaining compounds after releasing the fragrance molecules are mostly useless. Therefore, synthesizing a latent fragrance that is better in water solubility and remains in the solution system after releasing the fragrance also has a certain effect. Deodorant compounds become a technical problem to be solved.

SUMMARY OF THE INVENTION

The first object of the present invention is to provide a quaternary ammonium salt type hydrazide compound.

The second object of the present invention is to provide a preparation method of the quaternary ammonium salt type hydrazide compound.

The third object of the present invention is to provide a quaternary ammonium salt type hydrazone compound prepared from the quaternary ammonium salt type hydrazide compound and its application in the slow release of spices.

In order to achieve the above object, the technical scheme adopted in the present invention is as follows:

A first aspect of the present invention provides a quaternary ammonium salt type hydrazide compound having the following general formula:

R ¹ , R ² , R ³ are each independently selected from hydrogen, substituted or unsubstituted C ₁ -C ₂₀ alkyl; R ¹ , R ² , R ³ are 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:

A second aspect of the present invention provides a preparation method of the quaternary ammonium salt type hydrazide compound, comprising the following steps:

The molar ratio is 1:(1.01～2) (preferably 1:1.1) N,N-dimethylglycine ethyl ester and haloalkane are mixed and reacted, and the temperature is 20～60℃ for 1～48h to obtain quaternary Ammonium salt type ester compound;

The hydrazine hydrate is dissolved in the solvent, the mixture of the quaternary ammonium salt type ester compound obtained above and the solvent is added, and the mol ratio of hydrazine hydrate and the quaternary ammonium salt type ester compound is (5～15): 1 (preferably 10: 1), react to obtain a quaternary ammonium salt type hydrazide compound.

Described haloalkane 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 and toluene.

A third aspect of the present invention provides a quaternary ammonium salt type hydrazone compound, having the structure shown in formula I:

In formula I,

R ¹ , R ² , R ³ are each independently selected from hydrogen, C ₁ -C ₂₀ alkyl; R ¹ , R ² , R ³ are not hydrogen at the same time;

R ⁴ is selected from hydrogen, C ₁ -C ₂₀ alkyl;

R ⁵ is selected from hydrogen, substituted or unsubstituted aryl, C ₁ -C ₂₀ alkenyl substituted aryl;

R ⁴ and R ⁵ are not both hydrogen;

R ⁶ is hydrogen, C ₁ -C ₂₀ alkyl;

X is halogen (F, Cl, Br or I).

More preferably, in the formula I,

R ¹ , R ² , R ³ are each independently selected from hydrogen, C ₇ -C ₁₆ alkyl; R ¹ , R ² , R ³ are not hydrogen at the same time;

R ⁴ is selected from hydrogen, methyl;

R ⁵ is selected from hydrogen, substituted or unsubstituted phenyl, substituted or unsubstituted benzoheterocycle, C ₁ -C ₂₀ alkenyl substituted phenyl;

R ⁴ and R ⁵ are not both hydrogen;

R ⁶ is hydrogen, methyl;

X is Cl, Br.

More preferably, in the formula I,

R ¹ , R ² and R ³ are each independently selected from hydrogen and C ₁₂ H ₂₅ ; R ¹ , R ² and R ³ are not hydrogen at the same time;

R ⁴ is selected from hydrogen, C ₁ -C ₅ alkyl;

R ⁵ is selected from hydrogen,

R ⁴ and R ⁵ are not both hydrogen;

R ⁶ is hydrogen, methyl;

X is Br.

Most preferably, the quaternary ammonium salt type hydrazone compound is a kind of in the following structure:

A fourth aspect of the present invention provides a preparation method of the quaternary ammonium salt type hydrazone compound, comprising the following steps:

Dissolving a quaternary ammonium salt type hydrazide compound and an aldehyde or ketone fragrance in a molar ratio of 1:(1.1 to 2) (preferably 1:1.5) in a solvent, and performing a reflux reaction to obtain the quaternary ammonium salt type hydrazone compound .

The solvent is ethanol, methanol and toluene.

Described aldehyde or ketone class fragrance is cinnamaldehyde, new jasmonaldehyde, 4-phenyl-2-butanone, rabbit ear aldehyde, beta-ionone, citronellal, benzaldehyde, anisaldehyde, phenylacetaldehyde, Vanillin, lily aldehyde, privet aldehyde, menthone, cyclopentadecanone, acetophenone, p-methylacetophenone, p-methoxyacetophenone, tonal musk, damascenone, pentyl ring Pentanone, apigenone.

The fifth aspect of the present invention provides an application of the quaternary ammonium salt type hydrazone compound in the slow release of fragrance.

The sixth aspect of the present invention provides the use as a fragrance sustained-release agent.

Owing to adopting the above-mentioned technical scheme, the present invention has the following advantages and beneficial effects:

The quaternary ammonium salt type hydrazone compound with long carbon chain prepared by the invention has excellent water solubility and good surface activity, and is a kind of multifunctional surfactant with slow-release aroma effect. The synthetic method used in the present invention has simple steps and relatively mild reaction conditions. The synthesized quaternary ammonium salt type hydrazide compound can react with aldehydes and ketones in aqueous solution, and also has good surface activity. If it is used in combination with some weakly acidic washing products, it not only has the ability to reduce The surface tension ability of water can also make the fragrance in the washing product last longer, so it has a certain market application prospect.

Description of drawings

Figure 1 is a schematic diagram of a surface tension-concentration curve of a quaternary ammonium salt type hydrazide compound.

Figure 2 is a schematic diagram of the equilibrium process of hydrolysis and formation of hydrazone compounds in pH 4.5 citrate buffer tested by UV-Vis spectroscopy.

Figure 3 is a schematic diagram of the equilibrium process of hydrolysis and formation of hydrazone compounds in pH 2.5 phosphate buffer solution tested by UV-Vis spectroscopy.

Fig. 4 is a schematic diagram showing the time-concentration curve of cinnamaldehyde released by quaternary ammonium salt type hydrazone compound A and pure fragrance substances.

Fig. 5 is a schematic diagram of the time-concentration curve of the release of neojasmonal from quaternary ammonium salt-type hydrazone compound B and pure fragrance substances.

Figure 6 is a schematic diagram showing the time-concentration curves of quaternary ammonium salt-type hydrazone compound C and pure fragrance substances releasing 4-phenyl-2-butanone.

Fig. 7 is a schematic diagram showing the time-concentration curve of quaternary ammonium salt type hydrazone compound D and pure fragrance substance releasing oxalin.

Detailed ways

In order to illustrate the present invention more clearly, the present invention will be further described below with reference to the preferred embodiments. Those skilled in the art should understand that the content specifically described below is illustrative rather than restrictive, and should not limit the protection scope of the present invention.

Example 1

The preparation method of quaternary ammonium salt type hydrazone compound comprises the following steps:

(1) Add 0.65g (5mmol) N,N-dimethylglycine ethyl ester to the reaction tube, add 1.37g (5.5mmol) bromododecane, react under the condition that no solvent is added and the temperature is 40°C Reaction for 24h. After the reaction, anhydrous ether was added to the reaction tube for washing, and the lower layer was an oily liquid after standing, and the oily liquid was separated, and washed twice with ether, and recrystallized with ether to obtain a white quaternary ammonium salt type ester compound, Yield was 70%.

(2) Weigh 0.25g (5mmol) of hydrazine hydrate and dissolve it in 15mL of ethanol, dissolve 0.2g (0.5mmol) of the quaternary ammonium salt type ester compound obtained in the previous step in 10mL of ethanol, and then slowly add it to the ethanolic solution of hydrazine hydrate , the reaction was carried out at room temperature for 6 h. After the reaction was finished, the ethanol solvent was removed under reduced pressure, put into a refrigerator for overnight cooling, a white solid was precipitated, and the suction filtration was washed with glacial ethanol to obtain a quaternary ammonium salt type hydrazide compound (structure shown in formula 3a), and the yield was was 83%.

¹ H NMR (400 MHz, CDCl ₃ ) δ 4.65 (s, 2H), 3.65 (dd, J=10.2, 6.7 Hz, 2H), 3.44 (s, 6H), 1.79 (s, 2H), 1.31 (d, J=40.6Hz, 20H), 0.88(t, J=6.8Hz, 3H).

(3) 0.384g (0.8mmol) of synthesized quaternary ammonium salt type hydrazide compound was added to the round-bottomed flask, 0.158g (1.2mmol) of cinnamaldehyde was added, and finally 15mL of ethanol was added as a solvent for reflux reaction for 4h. After the reaction was completed, it was cooled to room temperature and separated by column chromatography using petroleum ether/ethyl acetate as the eluent to obtain a pale yellow target product (structure shown in formula A) with a yield of 78%.

¹ H NMR (400 MHz, CDCl ₃ ) δ 12.61 (s, 1H), 8.35 (d, J=8.4 Hz, 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 quaternary ammonium salt type hydrazone compound comprises the following steps:

Except that the cinnamaldehyde in step (3) of Example 1 was changed to new jasmonaldehyde, other conditions were the same as those described in Example 1, and the compound represented by formula B was obtained.

¹ H NMR (400 MHz, CDCl ₃ ) δ 12.29 (s, 1H), 7.86 (d, J=6.2 Hz, 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 quaternary ammonium salt type hydrazone compound comprises the following steps:

Except that the cinnamaldehyde in step (3) of Example 1 was changed to 4-phenyl-2-butanone, other conditions were the same as those described in Example 1, and the compound represented by formula C was obtained.

¹ H NMR (400 MHz, CDCl ₃ ) δ 7.29 (d, J=6.8 Hz, 2H), 7.19 (t, J=7.9 Hz, 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 quaternary ammonium salt type hydrazone compound comprises the following steps:

Except that the cinnamaldehyde in step (3) of Example 1 was changed to oxalic aldehyde, other conditions were the same as those described in Example 1, and the compound represented by formula D was obtained.

¹ H NMR (400 MHz, CDCl ₃ ) δ 7.88 (d, J=6.2 Hz, 1H), 7.11 (dd, J=22.5, 8.1 Hz, 4H), 4.65 (d, J=3.1 Hz, 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

Test of surface tension of quaternary ammonium hydrazide compounds:

According to the methods of steps (1) and (2) in Example 1, carbon chain lengths of 7 (structure shown in formula 1a), 10 (structure shown in formula 2a), 12 (structure shown in formula 3a) were synthesized , 14 (structure shown in formula 4a), 16 (structure shown in formula 5a) and long fluorine chain quaternary ammonium salt type hydrazide compounds (structure shown in formula 6a), these compounds all have good properties in water Solubility. In the process of testing the surface tension, take 40 mL of water as the benchmark, and gradually add the prepared sample solution with a concentration of 0.01 mol/L to be tested. Finally, take the logC of the added sample concentration as the abscissa, and the surface tension value of water as the ordinate. surface tension-concentration curves.

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 ) δ 4.62(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 (400 MHz, CDCl ₃ ) δ 4.65 (s, 2H), 3.65 (dd, J=10.2, 6.7 Hz, 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 ) δ 4.63(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 ) δ 3.98(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:[MI] ⁺ Calcd for C ₁₄ H ₁₅ F ₁₇ N ₃ O 569.0944; Found 569.0941.

The test results are shown in Figure 1, which is a schematic diagram of the surface tension-concentration curve of the quaternary ammonium salt-type hydrazide compound. It can be seen from the figure that when the carbon chain length is 7, the surface tension of water after adding the sample to be tested There is not much change, indicating that this compound has no surface activity. The addition of other compounds can effectively reduce the surface tension of water. It can be seen that when the carbon chain length increases from 7 to 12, the surface activity gradually increases, but when the length of the carbon chain continues to increase to 14 and 16, it reduces the water surface. The ability to tension gradually diminishes. When the carbon chain length is 12, it can reduce the surface tension of water to about 18.68mN/m, indicating that it is a good surfactant. At the same time, a quaternary ammonium salt type hydrazide compound with a long fluorine chain was also synthesized, which can reduce the surface tension of water to about 31.53 mN/m, indicating that it also has a certain surface activity, but the effect is general. According to the test of surface tension, the hydrazide compound has the best surface activity when the carbon chain length is 12. In the following, it is used as a matrix to react with perfume aldehydes and ketones to generate corresponding hydrazone compounds, and then the performance of releasing perfume is tested.

Example 6

Hydrolysis and formation kinetic equilibrium test of quaternary ammonium hydrazone compounds:

The quaternary ammonium hydrazones are hydrolyzed to release fragrance aldehydes and ketones under acidic conditions. In order to explore the conditional properties of quaternary ammonium hydrazones to release fragrances, and the hydrolysis rates of quaternary hydrazones in different acidic aqueous solutions, The hydrolysis and formation kinetic equilibrium were tested by UV-visible spectrophotometer, because UV-visible spectrophotometer can not only measure the maximum absorption wavelength of the compound to determine the structure of the compound, but also can determine the structure of the compound by measuring the reaction sample. The solution is measured by repeated dynamic spectra, and the structure and concentration changes of the compounds during the reaction are tracked in real time. A hydrazide compound with a carbon length of 12 (the structure is shown in formula 3a), vanillin and hydrazone compounds synthesized from them were selected for kinetic analysis.

To prepare buffer solutions of different acids:

Preparation of citric acid buffer solution with pH of 4.5: Weigh 0.65g sodium hydroxide, 0.62g sodium chloride and 2.58g citric acid in turn, dissolve in 160.02g deionized water, add 31.45g absolute ethanol to make a solution, take the above Add 2 mL of absolute ethanol to 10 mL of the prepared solution to prepare a citric acid buffer solution with a volume ratio of water and ethanol of 2:1 and a pH of 4.5.

Preparation of phosphate buffer solution with pH of 2.5: Weigh 1.97g of phosphoric acid, 1.37g of potassium dihydrogen phosphate and 0.6g of sodium chloride respectively, dissolve them in 160.01g of water, add 31.45g of absolute ethanol to make a solution, and take the prepared solution. Add 2 mL of absolute ethanol to 10 mL of the solution to prepare a phosphate buffer solution with a volume ratio of water and ethanol of 2:1 and a pH of 2.5.

Test of UV-Vis spectrum: The test cuvette used is a 3mL quartz cuvette, and 0.2mL of hydrazide compound and 0.2mL of vanillin (both substances are formulated into 2.0×10 ^-4 mol/L ethanol solution) are added To the cuvette, add 1.6 mL of pH 4.5 citric acid buffer to prepare a solution with a volume ratio of water and ethanol of 2:1 and a concentration of 1.7×10 ^-5 mol/L. The prepared solution was tested two minutes later, and the test time interval was 30 minutes. The test mainly focused on the formation process of hydrazone compounds at pH 4.5. The dosage of hydrazone compounds in the cuvette was changed to 0.4 mL (configured into 1.0×10 ^-4 mol/L ethanol solution), and then 1.6 mL of pH 4.5 citric acid buffer was added for the test, and the time interval was also 30 min. Finally, the above-mentioned citrate buffer with pH of 4.5 was replaced with phosphate buffer with pH of 2.5 to carry out the above two tests. The time interval of the test was 5min. The obtained UV-Vis spectra are shown in Figures 2 and 3. Figure 2 It is a schematic diagram of the equilibrium process of the hydrolysis and formation of hydrazone compounds in pH 4.5 citric acid buffer tested by UV-Vis spectroscopy. Figure 3 shows the hydrolysis and formation of hydrazone compounds in pH 2.5 phosphate buffer solution by UV-Vis spectroscopy. Schematic diagram of the equilibrium process.

As shown in Figure 2, the following curve represents the process of the formation of hydrazone compounds in acidic aqueous solution by hydrazide compound and vanillin mixture. The absorbance gradually increases with time. It can also be seen from the figure that the absorbance increases The amplitude is getting smaller and smaller, indicating that the reaction proceeds relatively fast at the beginning, and finally gradually slows down to reach equilibrium; the above curve represents the hydrolysis process of hydrazone compounds, and the absorbance gradually decreases with time. Achieve balance. The figure more intuitively reflects that the hydrazide compound and vanillin can react in the mixed acidic aqueous solution of water and ethanol.

As shown in Figure 3, it is the kinetic equilibrium process of hydrolysis and formation of hydrazone compounds in a relatively acidic aqueous solution. It can be seen from the figure that the hydrolysis and formation rates of hydrazone compounds in a relatively acidic aqueous solution are very fast. Quick and easy to balance. Comparing Figure 2 and Figure 3, it can be found that hydrazone compounds are more likely to be hydrolyzed under more acidic conditions, and the reaction between hydrazide compounds and vanillin to generate hydrazones is also more acidic, the faster the reaction.

Two conclusions can be drawn from the above; the synthesized new quaternary ammonium salt-type hydrazide compound (compound 3a) can carry out equilibrium reaction with vanillin in an acidic aqueous solution, which has a certain positive significance for the slow-release application of fragrance substances. The rate of hydrolysis of hydrazones to release aldehydes and ketones is slower under weaker acidic conditions, which provides a theoretical basis for the sustained-release effect of the following tests of hydrazones.

Example 7

Detection of aldehyde and ketone fragrance substances released by quaternary ammonium hydrazone compounds on the surface of cotton cloth:

The testing of fragrance substances released by latent fragrance molecules on the surface of cotton cloth is a conventional test method, which can simulate the environmental state of latent fragrance compounds in practical applications, and is conducive to evaluating the quality of latent fragrance release performance. . In this experiment, solid-phase microextraction-gas chromatography was used to detect the concentration of fragrance substances released by hydrazone compounds on the surface of cotton cloth and the concentration of fragrance substances released by equimolar pure fragrance molecules on the surface of cotton cloth. Hydrazone compounds have the effect of controlling and delaying the release of fragrance substances.

In many washing products, fragrance substances are mixed with surfactants. One of them is a cationic surfactant that is used as a fabric softener. The fabric softener can not only adhere to the clothes well, but also can To promote some non-polar organic small molecules such as fragrance substances can also be well adsorbed on cotton clothes, so in the process of the experiment, triethanolamine fatty acid ester quaternary ammonium salt was added as a fabric softener, which is a new type of fabric softener. Fabric softener with excellent softness, antistatic, rewetting and biodegradability.

The specific test method is: first add 1.8g triethanolamine fatty acid ester quaternary ammonium salt to 50mL deionized water, stir evenly, add ethanol in which 0.01mol quaternary ammonium salt type hydrazone compounds (A, B, C, D) are dissolved A solution of 5 mL or 0.01 mol of cinnamaldehyde, new jasmonaldehyde, 4-phenyl-2-butanone or rabbit ear aldehyde was added with citric acid to adjust the pH of the solution to 3.1, and allowed to stand for 12 hours to achieve dynamic equilibrium. Then add deionized water to adjust the pH of the solution to 4.0-4.2, immerse a piece of 12×12cm cotton cloth in the solution and stir mechanically for 10 minutes, and then let it stand for 5 minutes to promote the adsorption of hydrazone compounds and fragrance substances on the cotton cloth, and then twist it by hand. Dry and dry overnight in the natural state. Dissolve 2mL of pH 4.5 acid (0.65g of sodium hydroxide, 0.62g of sodium chloride and 2.58g of citric acid in 160.02g of deionized water, then add 31.45g of ethanol to make a solution, take 10mL of the above prepared solution Add 2 mL of absolute ethanol to prepare a citric acid buffer solution with a water-ethanol volume ratio of 2:1 and a pH of 4.5) and spray the aqueous solution evenly on the cotton cloth. Cut the cotton cloth into small pieces and put them in a 20 mL headspace bottle. 20 μL of o-dichlorobenzene (100 ppm) was added as an internal standard and sealed for solid-phase microextraction.

Solid phase microextraction operating conditions: Before using SPME to extract the fiber head, the fiber head should be aged to remove the residual organic matter on the fiber head to prevent error interference. Aging at 250°C for 30min, insert the aged extraction fiber tip into the headspace part of the sample bottle (note: do not let the extraction tip come into contact with the substance to be tested, to avoid breaking and contaminating the extraction tip), the temperature is 35°C Extraction for 1h under the conditions of 1 hour, take out the extraction fiber head after the extraction, insert the needle into the injection port of the gas chromatograph quickly, safely push out the fiber head, thermally decompose the adsorbed aroma components, the desorption time is 5min, and start the gas chromatograph at the same time Conduct data collection and analysis.

Taking the time as the abscissa and the concentration of the released aroma substances as the ordinate, a schematic diagram of the time-concentration curve is obtained, as shown in Figures 4 to 7, Figure 4 is the release of cinnamaldehyde by the quaternary ammonium salt type hydrazone compound A and pure fragrance substances Schematic diagram of the time-concentration curve of the quaternary ammonium salt type hydrazone compound B and the release of the new jasmonal from pure fragrance substances, Fig. 6 is the release of the quaternary ammonium salt type hydrazone type compound C and the pure fragrance substance. Schematic diagram of the time-concentration curve of 4-phenyl-2-butanone, and Fig. 7 is a schematic diagram of the time-concentration curve of the quaternary ammonium salt type hydrazone compound D and the pure fragrance substance releasing oxalin.

It can be seen from Figures 4 to 7 that the concentration of fragrance released by all quaternary ammonium salt-type hydrazone compounds is greater than that of pure fragrance substances, which is mainly caused by two processes. After adding the quaternary ammonium salt type hydrazone compound, it will be equilibrated for 12 hours. During the equilibrium process, the quaternary ammonium salt type hydrazone type compound will be partially hydrolyzed, some of the fragrance substances will be volatilized, and some of the fragrance substances will reach a kind of hydrazide in the aqueous solution. Dynamic equilibrium state; while pure fragrance substances will slowly volatilize at the beginning because they are not covalently linked with other substances. Another process is the drying process in which the quaternary ammonium hydrazone compounds and fragrance substances are adsorbed on the cotton cloth. As the water continues to evaporate during the drying process, the rate of hydrolysis of the quaternary ammonium hydrazone compounds is also decreasing. The fragrance substances in the air are small; pure fragrance substances will always volatilize. In the presence of moisture, the volatilization of water will reduce the temperature of the cotton cloth and slow down the release of the fragrance substances. When the water evaporates, the fragrance substances on the cotton The rate of diffusion into the air will be further accelerated, and for these two reasons, the volatile concentration of pure fragrance substances is always lower than that released by quaternary ammonium hydrazone compounds.

By comparing Figures 4 to 7, it can be found that the quaternary ammonium salt type hydrazone compound C released the highest concentration of fragrance substances, while the corresponding pure fragrance substance 4-phenyl-2-butanone released the lowest concentration. This phenomenon The reason is that the boiling point of 4-phenyl-2-butanone is relatively low. Due to the low boiling point, the pure fragrance molecules volatilize more on the cotton cloth, resulting in a very low volatilization concentration during the test; and the quaternary ammonium salt type hydrazone The 4-phenyl-2-butanone released after the hydrolysis of compound C can quickly volatilize into the air, making its concentration in the headspace bottle relatively high. Compared with Figures 4 and 7, it is found that the volatile concentration of pure new jasmonal is higher than that of other aldehydes and ketones. The main reason is that the boiling point of new jasmonal is 134-135 °C, the boiling point is high, and its volatility relatively low, resulting in a relatively large amount of it remaining on the cotton. It can be found through experiments that hydrazone compounds can delay the volatilization of fragrance substances by about 10 times. It can be concluded from this that the quaternary ammonium salt type hydrazone compounds (Examples 1-4) prepared in this application can control and delay the release of fragrance substances. conclusion.

The quaternary ammonium salt type hydrazone compound prepared in the present application can not only be hydrolyzed in aqueous solution to release aldehyde and ketone fragrance substances, but also the quaternary ammonium salt type hydrazide compound left in the solution system after hydrolysis also has good surface activity. When some weakly acidic washing products are used together, they not only have the ability to reduce the surface tension of water, but also make the fragrance in the washing products last longer. Therefore, they have certain market application prospects.

The above descriptions are only preferred embodiments of the present invention, and are not intended to limit the present invention in any form. Although the present invention has been disclosed above with preferred embodiments, it is not intended to limit the present invention. Within the scope of the technical solution of the present invention, personnel can make some changes or modifications to equivalent examples of equivalent changes by using the above-mentioned technical content, but any content that does not depart from the technical solution of the present invention is based on the technical solution of the present invention. Substantially any simple modifications, equivalent changes and modifications made to the above embodiments still fall within the scope of the solutions of the present invention.

Claims (5)

1. a quaternary ammonium salt type hydrazone compound, is characterized in that, has structure shown in formula I:

In formula I, R ¹ , R ² , R ³ are each independently selected from hydrogen, C ₁ -C ₂₀ alkyl; R ¹ , R ² , R ³ are not hydrogen at the same time; R ⁴ is selected from hydrogen, C ₁ -C ₂₀ alkyl; R ⁵ is selected from hydrogen,

R ⁴ and R ⁵ are not both hydrogen; R ⁶ is selected from hydrogen, C ₁ -C ₂₀ alkyl; X is halogen. 2. quaternary ammonium salt type hydrazone compound according to claim 1, is characterized in that, in described formula I, R ¹ , R ² , R ³ are each independently selected from hydrogen, C ₇ -C ₁₆ alkyl; R ¹ , R ² , R ³ are not hydrogen at the same time; R ⁴ is selected from hydrogen, methyl; R ⁵ is selected from hydrogen,

R ⁴ and R ⁵ are not both hydrogen; R ⁶ is selected from hydrogen, methyl; X is Cl or Br. 3. quaternary ammonium salt type hydrazone compound according to claim 2, is characterized in that, in described formula I, R ¹ , R ² and R ³ are each independently selected from hydrogen and C ₁₂ H ₂₅ ; R ¹ , R ² and R ³ are not hydrogen at the same time; R ⁴ is selected from hydrogen, C ₁ -C ₅ alkyl; R ⁴ and R ⁵ are not both hydrogen; R ⁶ is selected from hydrogen, methyl; X is Br. 4. quaternary ammonium salt type hydrazone compound according to claim 3, is characterized in that, described quaternary ammonium salt type hydrazone type compound is a kind of in following structure:

5. the application of the quaternary ammonium salt type hydrazone compound described in any one of claim 1 to 4 as fragrance sustained-release agent.

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