阅读说明：本技术 酯类化合物及其制备方法及应用 (Ester compound and preparation method and application thereof ) 是由 于泳飞 钟能帮 吴奇林 蔡国祥 关俊健 于 2021-01-29 设计创作，主要内容包括：本发明提供了一种酯类化合物,所述酯类化合物的结构式如式(1)所示；在式(1)中,X每次出现,独立选自具有1～4个碳原子的烷基。该酯类化合物具有佛手柑香气,且留香持久,可作为体香和基香应用于香精配方中,在日化调香领域中具有广泛的应用前景。(The invention provides an ester compound, wherein the structural formula of the ester compound is shown as a formula (1); in formula (1), X is independently selected from alkyl groups having 1 to 4 carbon atoms at each occurrence. The ester compound has bergamot fragrance and lasting fragrance, can be used as body fragrance and base fragrance to be applied to essence formulas, and has wide application prospect in the field of daily chemical blending.)

1. An ester compound, wherein the structural formula of the ester compound is shown as formula (1):

in formula (1), X is independently selected from alkyl groups having 1 to 4 carbon atoms at each occurrence.

2. An ester compound according to claim 1, wherein each occurrence of X is independently selected from alkyl groups having 3 to 4 carbon atoms.

3. Use of the ester compound according to any one of claims 1 to 2 for the preparation of a perfume.

4. The preparation method of the ester compound according to any one of claims 1 to 2, wherein the ester compound is prepared by subjecting a compound A to a hydroboration oxidation reaction;

the compound A has a structure shown in a formula (2):

in the formula (2), X is as defined in any one of claims 1 to 2.

5. The method for preparing an ester compound according to claim 4, wherein the hydroboration oxidation reaction comprises the following steps:

carrying out addition reaction on the compound A and a borohydride, then carrying out oxidation reaction on a product obtained after the addition reaction and a compound D, distilling after the oxidation reaction is finished, and collecting a first fraction;

the compound D is hydrogen peroxide or tert-butyl hydroperoxide.

6. The method for preparing an ester compound according to claim 5, wherein the molar ratio of the borohydride compound, the compound A and the compound D is (0.5-1): 1 (1-1.5).

7. The method for preparing ester compounds according to claim 5, wherein the temperature of the addition reaction is 15-30 ℃, and the time of the addition reaction is 1.5-2.5 h; and/or

The temperature of the oxidation reaction is 15-30 ℃, and the time of the oxidation reaction is 0.5-1.5 h.

8. The method for preparing ester compound according to claim 5, wherein collecting the first fraction is collecting a fraction of mother liquor at 120-140 ℃.

9. The method for preparing the ester compound according to any one of claims 4 to 8, wherein the compound A is prepared by performing an ester exchange reaction between the compound B and the compound C;

the compound B has a structure represented by formula (3):

the compound C has a structure represented by formula (4):

10. the method for preparing the ester compound according to claim 9, wherein the molar ratio of the compound B to the compound C is (1-2): 1; the temperature of the ester exchange reaction is 100-120 ℃, and the time of the ester exchange reaction is 3-5 h.

Technical Field

The invention relates to the technical field of chemical industry, in particular to an ester compound and a preparation method and application thereof.

Background

Bergamot is the fruit of bergamot of Rutaceae, and its name is obtained because the top of the fruit is open like fingers. The bergamot smells like citrus, but is different from citrus fragrance in that the bergamot also has light special flowery scent and bitter taste, is more mellow and full in smell, and has the quality of coolness, freshness and refreshing. Therefore, bergamot has wide application in the field of flavoring.

The essence and spice with bergamot fragrance are traditionally prepared by extracting from bergamot fruits, the bergamot fruits are rich in various aromatic substances, the main fragrant components of the bergamot fruits are linalool, myrcene, nerol, geraniol, carvacrol, dextro-carvone and other naturally occurring compounds in nature, but as most of the compounds are volatile light components and the fragrance of the compounds is lack of persistence, the traditional spice with the bergamot fragrance is mostly used for top fragrance in a flavoring formula and is rarely used for body fragrance or base fragrance.

Disclosure of Invention

Based on the above, the invention provides an ester compound, which has bergamot fragrance and has lasting fragrance.

The invention is realized by the following technical scheme.

An ester compound, wherein the structural formula of the ester compound is shown as formula (1):

in formula (1), X is independently selected from alkyl groups having 1 to 4 carbon atoms at each occurrence.

In one embodiment, each occurrence of X is independently selected from alkyl groups having 3 to 4 carbon atoms.

The invention also provides an application of the ester compound in preparation of essence.

The invention also provides a preparation method of the ester compound, wherein the ester compound is prepared by carrying out hydroboration oxidation reaction on the compound A;

the compound A has a structure shown in a formula (2):

in formula (2), X is as defined above.

In one embodiment, the hydroboration oxidation reaction comprises the following steps:

carrying out addition reaction on the compound A and a borohydride, then carrying out oxidation reaction on a product obtained after the addition reaction and a compound D, distilling after the oxidation reaction is finished, and collecting a first fraction;

the compound D is hydrogen peroxide or tert-butyl hydroperoxide.

In one embodiment, the molar ratio of the borohydride to the compound A to the compound D is (0.5-1): 1 (1-1.5).

In one embodiment, the temperature of the addition reaction is 15-30 ℃, and the time of the addition reaction is 1.5-2.5 h; and/or

The temperature of the oxidation reaction is 15-30 ℃, and the time of the oxidation reaction is 0.5-1.5 h.

In one embodiment, collecting the first fraction refers to collecting the fraction with the mother liquor temperature of 120-140 ℃.

In one embodiment, the compound A is prepared by performing ester exchange reaction on the compound B and the compound C;

the compound B has a structure represented by formula (3):

the compound C has a structure represented by formula (4):

in one embodiment, the molar ratio of the compound B to the compound C is (1-2): 1; the temperature of the ester exchange reaction is 100-120 ℃, and the time of the ester exchange reaction is 3-5 h.

Compared with the prior art, the ester compound has the following beneficial effects:

the ester compound provided by the invention is an ester compound containing dimethyl and hydroxyl, has bergamot fragrance, is long in fragrance retention time, can be used as a body fragrance and a base fragrance to be applied to an essence formula, and has a wide application prospect in the field of daily chemical blending.

Drawings

FIG. 1 is a gas chromatogram of 8-hydroxy-2, 6-dimethyloctyl-2-butyrate provided in example 1 of the present invention;

FIG. 2 is a nuclear magnetic resonance hydrogen spectrum of 8-hydroxy-2, 6-dimethyloctyl-2-butyrate provided in example 1 of the present invention;

FIG. 3 is the NMR carbon spectrum of 8-hydroxy-2, 6-dimethyloctyl-2-butyrate provided in example 1 of the present invention.

Detailed Description

To facilitate an understanding of the invention, the invention will now be described more fully with reference to the accompanying drawings. The present invention may be embodied in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.

The invention provides an ester compound, the structural formula of which is shown as the formula (1):

in formula (1), X is independently selected from alkyl groups having 1 to 4 carbon atoms at each occurrence.

In a specific example, each occurrence of X is independently selected from the group consisting of alkyl groups having 3 to 4 carbon atoms; preferably, X is selected from butyl.

The invention also provides an application of the ester compound in preparation of essence. Specifically, the ester compound provided by the invention can be used as a body fragrance and a base fragrance in a formula of the essence, wherein the essence comprises daily necessities essence, cosmetic essence, tobacco essence, food essence and the like, and is not limited herein.

The invention also provides a preparation method of the ester compound, wherein the ester compound is prepared by carrying out hydroboration oxidation reaction on the compound A;

compound a has the structure shown in formula (2):

in formula (2), X is independently selected from alkyl groups having 1 to 4 carbon atoms at each occurrence.

In a specific example, each occurrence of X is independently selected from the group consisting of alkyl groups having 3 to 4 carbon atoms; preferably, X is selected from butyl.

In one specific example, the hydroboration oxidation reaction comprises the steps of:

carrying out addition reaction on the compound A and a boron hydride, then carrying out oxidation reaction on a product obtained after the addition reaction and the compound D, distilling after the oxidation reaction is finished, and collecting a first fraction;

the compound D is hydrogen peroxide or tert-butyl hydroperoxide.

In a specific example, the molar ratio of the borohydride compound to the compound A to the compound D is (0.5-1): 1 (1-1.5).

In a specific example, the temperature of the addition reaction is 15 ℃ to 30 ℃, and the time of the addition reaction is 1.5h to 2.5 h.

It is understood that, in the present application, the temperature of the addition reaction includes, but is not limited to, the following temperatures: 15 deg.C, 16 deg.C, 17 deg.C, 18 deg.C, 19 deg.C, 20 deg.C, 21 deg.C, 22 deg.C, 23 deg.C, 24 deg.C, 25 deg.C, 26 deg.C, 27 deg.C, 28 deg.C, 29 deg.C and 30 deg.C; preferably, the temperature of the addition reaction is 25 ℃.

It is understood that, in the present application, the time of the addition reaction includes, but is not limited to, 1.5h, 1.6h, 1.7h, 1.8h, 1.9h, 2h, 2.1h, 2.2h, 2.3h, 2.4h and 2.5 h; preferably, the time of the addition reaction is 2 h.

In a specific example, the temperature of the oxidation reaction is 15 ℃ to 30 ℃, and the time of the oxidation reaction is 0.5h to 1.5 h.

It is to be understood that in the present application, the temperature of the oxidation reaction includes, but is not limited to, the following temperatures: 15 deg.C, 16 deg.C, 17 deg.C, 18 deg.C, 19 deg.C, 20 deg.C, 21 deg.C, 22 deg.C, 23 deg.C, 24 deg.C, 25 deg.C, 26 deg.C, 27 deg.C, 28 deg.C, 29 deg.C and 30 deg.C; preferably, the temperature of the oxidation reaction is 25 ℃.

It is understood that in the present application, the time of the oxidation reaction includes, but is not limited to, 0.5h, 0.6h, 0.7h, 0.8h, 0.9h, 1h, 1.1h, 1.2h, 1.3h, 1.4h, and 1.5 h; preferably, the time of the addition reaction is 1 h.

In a specific example, collecting the first fraction refers to collecting the fraction with the mother liquor temperature of 120-140 ℃; preferably, collecting the first fraction means collecting the fraction with the mother liquor temperature of 128 ℃ to 133 ℃.

Collecting the fraction with the mother liquor temperature of 120-140 ℃ refers to collecting the fraction with the liquid temperature of 120-140 ℃.

In a specific example, compound a is prepared by transesterification of compound B with compound C;

compound B has the structure shown in formula (3):

compound C has the structure shown in formula (4):

in a specific example, the molar ratio of the compound B to the compound C is (1-2): 1; it is understood that, in the present application, the molar ratio of compound B to compound C includes, but is not limited to, 1.1:1, 1.2:1, 1.3:1, 1.4:1, 1.5:1, 1.6:1, 1.7:1, 1.8:1, 1.9:1, and 2.0: 1.

In a specific example, the temperature of the transesterification reaction is 100 ℃ to 120 ℃, and the time of the transesterification reaction is 3h to 5 h.

As will be appreciated, in the present application, the temperature of the transesterification reaction includes, but is not limited to, 100 ℃, 101 ℃, 102 ℃, 103 ℃, 104 ℃, 105 ℃, 106 ℃, 107 ℃, 108 ℃, 109 ℃, 110 ℃, 111 ℃, 112 ℃, 113 ℃, 114 ℃, 115 ℃, 116 ℃, 117 ℃, 118 ℃, 119 ℃ and 120 ℃.

It is understood that in the present application, the time of the transesterification reaction includes, but is not limited to, 3h, 3.1h, 3.2h, 3.3h, 3.4h, 3.5h, 3.6h, 3.7h, 3.8h, 3.9h, 4h, 4.1h, 4.2h, 4.3h, 4.4h, 4.5h, 4.6h, 4.7h, 4.8h, 4.9h and 5 h; preferably, the transesterification reaction time is 4 h.

In a specific example, the method further comprises the following steps after the transesterification reaction is finished: distilling and collecting a second fraction.

In a specific example, collecting the second fraction refers to collecting the fraction with the steam temperature of 100-120 ℃; preferably, collecting the second fraction means collecting the fraction with the steam temperature of 108-111 ℃.

Collecting the fraction with the steam temperature of 100-120 ℃ refers to collecting the fraction with the gas temperature of 100-120 ℃.

In a more specific example, the preparation method of the ester compound comprises the following steps:

s1: will be provided withAndcarrying out ester exchange reaction; the temperature of the ester exchange reaction is 100-120 ℃, and the time of the ester exchange reaction is 3-5 h; distilling after the ester exchange reaction is finished, and collecting a second fraction with the steam temperature of 100-120 ℃ to obtain a compound AX is independently selected from alkyl with 1-4 carbon atoms at each occurrence;

s2: carrying out addition reaction on the compound A and a boron hydride at the temperature of 15-30 ℃ for 1.5-2.5 h; then, carrying out oxidation reaction on the product after the addition reaction and hydrogen peroxide or tert-butyl hydroperoxide, wherein the temperature of the oxidation reaction is 15-30 ℃, and the time of the oxidation reaction is 0.5-1.5 h; distilling after the oxidation reaction is finished, and collecting a first fraction of which the mother liquor temperature is 120-140 ℃.

The ester compound and the preparation method thereof according to the present invention will be described in further detail with reference to the following specific examples. The starting materials used in the following examples are all commercially available products unless otherwise specified.

Example 1

The embodiment provides an ester compound and a preparation method thereof, and the preparation method specifically comprises the following steps:

s1: 1563g of dihydromyrcenol, 2373g of butyric anhydride and 3L of toluene are sequentially added into a 20L reaction kettle, and after uniform stirring, the temperature is raised to 110 ℃ for reaction for 4 hours. Under the pressure of 400Pa, the fraction with the vapor temperature of 108-111 ℃ is collected to obtain 2105g of 2, 6-dimethyl-7-octene-2-butyrate.

S2: 226.4g of 2, 6-dimethyl-7-octene-2-butyrate, 200mL of dry tetrahydrofuran, and 500mL of a 1mol/L solution of diborane in tetrahydrofuran were added dropwise in this order to a 5L reactor, and the reaction was carried out at room temperature for 2 hours. Then, while maintaining the temperature at room temperature, 650mL of a 1mol/L aqueous solution of sodium hydroxide was added, followed by dropwise addition of 112mL of a 9.79mol/L aqueous solution of hydrogen peroxide, and the reaction was carried out at room temperature for 1 hour. Concentrating the mother liquor, filtering to remove filter residue, distilling the mother liquor under the pressure of 350Pa, and collecting the fraction of the mother liquor with the temperature of 128-133 ℃ to obtain 205.4g of 8-hydroxy-2, 6-dimethyl octyl-2-butyrate.

The 8-hydroxy-2, 6-dimethyl octyl-2-butyrate is detected by gas chromatography, and the chromatogram is shown in figure 1.

The nuclear magnetic resonance detection of 8-hydroxy-2, 6-dimethyl octyl-2-butyrate is carried out, the nuclear magnetic resonance hydrogen spectrum is shown in figure 2, the nuclear magnetic resonance carbon spectrum is shown in figure 3, and the specific NMR spectral characteristics are shown as follows:

¹H NMR(400MHz，CD₃Cl)：3.82(t，2H，J＝4.8Hz)，3.62(m，1H)，2.34(t，2H，J＝4.4Hz)，1.84-1.74(m，2H)，1.71-1.59(m，1H)，1.51-1.22(m，14H)，0.96-0.82(m，6H)。

³C NMR(100MHz，CD₃Cl):173.0，82.5，60.4，41.9，40.1，37.6，36.3，29.4，26.3，21.7，20.9，18.4，13.7。

the mass spectrometry data were as follows:

MS(ESI,m/z)267.2(M+Na⁺) (ii) a The theoretical calculation data of the high-resolution electrospray ionization mass spectrum is [ C ]₁₄H₂₈NaO₃]⁺(M+Na⁺)267.1931, the actual measured value was 267.1943.

And performing effect verification experiments including fragrance evaluation and fragrance retention test.

The fragrance evaluation of the compound was carried out by 5 perfumers who worked for more than 5 years:

fragrance retention test: 2 pieces of fragrance smelling test paper are respectively dipped with 1g of bergamot extract and 1g of 8-hydroxy-2, 6-dimethyl octyl-2-butyrate. The test paper is placed on a fragrance smelling frame, 5 fragrance regulating operators smell the test paper once every 2 hours, and when the fragrance of the fragrance smelling test paper cannot be sensed by more than or equal to 2 fragrance regulating operators, the fragrance remaining time is recorded.

The fragrance retention test shows that the fragrance retention time of the bergamot extract is 34 hours, the 8-hydroxy-2, 6-dimethyl octyl-2-butyrate presents strong bergamot fragrance, and the fragrance retention time is 54 hours.

Example 2

The embodiment provides an ester compound and a preparation method thereof, and the preparation method specifically comprises the following steps:

s1: 1563g of dihydromyrcenol, 2794g of valeric anhydride and 3L of toluene are sequentially added into a 20L reaction kettle, stirred uniformly, heated to 110 ℃ and reacted for 4 hours. Under the pressure of 400Pa, the fraction with the vapor temperature of 113 ℃ and 117 ℃ is collected to obtain 2114g of 2, 6-dimethyl-7-octene-2-pentanoate.

S2: 240.4g of 2, 6-dimethyl-7-octene-2-pentanoate, 200mL of dry tetrahydrofuran, and 500mL of a 1mol/L solution of diborane in tetrahydrofuran were added to a 5L reaction kettle in this order, and the reaction was carried out at room temperature for 2 hours. Then, while maintaining the temperature at room temperature, 650mL of a 1mol/L aqueous solution of sodium hydroxide was added, followed by dropwise addition of 112mL of a 9.79mol/L aqueous solution of hydrogen peroxide, and the reaction was carried out at room temperature for 1 hour. Concentrating the mother liquor, filtering to remove filter residue, distilling the mother liquor under the pressure of 350Pa, and collecting the fraction of the mother liquor with the temperature of 132-138 ℃ to obtain 230.2g of 8-hydroxy-2, 6-dimethyl octyl-2-valerate.

Mass spectrometry data for 8-hydroxy-2, 6-dimethyloctyl-2-valerate are as follows:

MS(ESI,m/z)281.2(M+Na⁺) (ii) a The theoretical calculation data of the high-resolution electrospray ionization mass spectrum is [ C ]₁₄H₂₈NaO₃]⁺(M+Na⁺)281.2087, the actual measured value was 281.2075.

And performing effect verification experiments including fragrance evaluation and fragrance retention test.

The fragrance evaluation of the compound was carried out by 5 perfumers who worked for more than 5 years:

fragrance retention test: 1 piece of fragrance smelling test paper is dipped with 1g of 8-hydroxy-2, 6-dimethyl octyl-2-valerate. The test paper is placed on a fragrance smelling frame, 5 fragrance regulating operators smell the test paper once every 2 hours, and when the fragrance of the fragrance smelling test paper cannot be sensed by more than or equal to 2 fragrance regulating operators, the fragrance remaining time is recorded.

The fragrance retention test shows that the 8-hydroxy-2, 6-dimethyl octyl-2-valerate presents obvious bergamot fragrance, and the fragrance retention time is 58 hours.

Example 3

The embodiment provides an ester compound and a preparation method thereof, and the preparation method specifically comprises the following steps:

s1: 1563g of dihydromyrcenol, 1952g of propionic anhydride and 3L of toluene are added into a 20L reaction kettle in sequence, and after uniform stirring, the temperature is raised to 110 ℃ for reaction for 4 hours. The fraction with vapor temperature of 105 ℃ and 109 ℃ was collected under 400Pa to obtain 1982g of 2, 6-dimethyl-7-octene-2-propionate.

S2: 212.3g of 2, 6-dimethyl-7-octene-2-propionate was sequentially charged into a 5L reactor, 200mL of dry tetrahydrofuran was added, and 500mL of a 1mol/L solution of diborane in tetrahydrofuran was added dropwise and reacted at room temperature for 2 hours. Then, while maintaining the temperature at room temperature, 650mL of a 1mol/L aqueous solution of sodium hydroxide was added, followed by dropwise addition of 112mL of a 9.79mol/L aqueous solution of hydrogen peroxide, and the reaction was carried out at room temperature for 1 hour. The mother liquor was concentrated, filtered to remove the residue, the mother liquor was distilled at 350Pa, and the 130 ℃ fraction of the mother liquor was collected at 124 ℃ to give 202.4g of 8-hydroxy-2, 6-dimethyloctyl-2-propionate.

Mass spectrometry data for 8-hydroxy-2, 6-dimethyloctyl-2-propionate were as follows:

MS(ESI,m/z)253.2(M+Na⁺) (ii) a The theoretical calculation data of the high-resolution electrospray ionization mass spectrum is [ C ]₁₃H₂₆NaO₃]⁺(M+Na⁺)253.1774, the actual measured value was 253.1755.

And performing effect verification experiments including fragrance evaluation and fragrance retention test.

The fragrance evaluation of the compound was carried out by 5 perfumers who worked for more than 5 years:

fragrance retention test: 1 strip of fragrance-smelling test paper is dipped with 1g of 8-hydroxy-2, 6-dimethyl octyl-2-propionate. The test paper is placed on a fragrance smelling frame, 5 fragrance regulating operators smell the test paper once every 2 hours, and when the fragrance of the fragrance smelling test paper cannot be sensed by more than or equal to 2 fragrance regulating operators, the fragrance remaining time is recorded.

The fragrance retention test shows that the 8-hydroxy-2, 6-dimethyl octyl-2-propionate presents strong fragrance of bergamot and citrus, and the fragrance retention time is 48 hours.

Example 4

The embodiment provides an ester compound and a preparation method thereof, and the preparation method specifically comprises the following steps:

s1: 1563g of dihydromyrcenol, 1532g of acetic anhydride and 3L of toluene are sequentially added into a 20L reaction kettle, stirred uniformly, heated to 110 ℃ and reacted for 4 hours. Under the pressure of 400Pa, the fraction with the vapor temperature of 102-105 ℃ was collected to obtain 1869g of 2, 6-dimethyl-7-octene-2-acetate.

S2: 198.3g of 2, 6-dimethyl-7-octene-2-acetate, 200mL of dry tetrahydrofuran, and 500mL of a 1mol/L solution of diborane in tetrahydrofuran were added dropwise in this order to a 5L reactor, and the reaction was carried out at room temperature for 2 hours. Then, while maintaining the temperature at room temperature, 650mL of a 1mol/L aqueous solution of sodium hydroxide was added, followed by dropwise addition of 112mL of a 9.79mol/L aqueous solution of hydrogen peroxide, and the reaction was carried out at room temperature for 1 hour. The mother liquor was concentrated, filtered to remove the residue, and the mother liquor was distilled under 350Pa to collect a fraction at a temperature of 120 ℃ and 125 ℃ to obtain 187.4g of 8-hydroxy-2, 6-dimethyloctyl-2-acetate.

Mass spectrometry data for 8-hydroxy-2, 6-dimethyloctyl-2-acetate were as follows:

MS(ESI,m/z)221.2(M+Na⁺) (ii) a The theoretical calculation data of the high-resolution electrospray ionization mass spectrum is [ C ]₁₂H₂₂NaO₃]⁺(M+Na⁺)221.1512, the actual measured value was 221.1533.

And performing effect verification experiments including fragrance evaluation and fragrance retention test.

The fragrance evaluation of the compound was carried out by 5 perfumers who worked for more than 5 years:

fragrance retention test: 1 strip of fragrance-smelling test paper is dipped with 1g of 8-hydroxy-2, 6-dimethyl octyl-2-acetate. The test paper is placed on a fragrance smelling frame, 5 fragrance regulating operators smell the test paper once every 2 hours, and when the fragrance of the fragrance smelling test paper cannot be sensed by more than or equal to 2 fragrance regulating operators, the fragrance remaining time is recorded.

The aroma retention test shows that the 8-hydroxy-2, 6-dimethyl octyl-2-acetate presents strong bergamot and citrus aroma, and the aroma retention time is 40 hours.

Example 5

The embodiment provides an ester compound and a preparation method thereof, and the preparation method specifically comprises the following steps:

s1: 1703g of 2, 7-dimethyl-8-nonene-2-alcohol, 2373g of butyric anhydride and 3L of toluene are sequentially added into a 20L reaction kettle, and after uniform stirring, the temperature is raised to 110 ℃ for reaction for 4 hours. Under the pressure of 400Pa, the fraction with the vapor temperature of 112-115 ℃ is collected to obtain 2121g of 2, 7-dimethyl-8-nonene-2-butyrate.

S2: 240.4g of 2, 7-dimethyl-8-nonene-2-butyrate, 200mL of dry tetrahydrofuran, and 500mL of a 1mol/L tetrahydrofuran solution of diborane were added dropwise to a 5L reaction vessel, and the reaction was carried out at room temperature for 2 hours. Then, while maintaining the temperature at room temperature, 650mL of a 1mol/L aqueous solution of sodium hydroxide was added, followed by dropwise addition of 112mL of a 9.79mol/L aqueous solution of hydrogen peroxide, and the reaction was carried out at room temperature for 1 hour. Concentrating the mother liquor, filtering to remove filter residues, distilling the mother liquor under the pressure of 350Pa, and collecting the fraction of the mother liquor at the temperature of 131-136 ℃ to obtain 230.7g of 9-hydroxy-2, 7-dimethyl octyl-2-butyrate.

Mass spectrometry data for 9-hydroxy-2, 7-dimethyloctyl-2-butyrate were as follows:

MS(ESI,m/z)281.2(M+Na⁺) (ii) a The theoretical calculation data of the high-resolution electrospray ionization mass spectrum is [ C ]₁₅H₃₀NaO₃]⁺(M+Na⁺)281.2087, the actual measured value was 281.2071.

And performing effect verification experiments including fragrance evaluation and fragrance retention test.

The fragrance evaluation of the compound was carried out by 5 perfumers who worked for more than 5 years:

fragrance retention test: 1 strip of fragrance-smelling test paper is dipped with 1g of 9-hydroxy-2, 7-dimethyl octyl-2-butyrate. The test paper is placed on a fragrance smelling frame, 5 fragrance regulating operators smell the test paper once every 2 hours, and when the fragrance of the fragrance smelling test paper cannot be sensed by more than or equal to 2 fragrance regulating operators, the fragrance remaining time is recorded.

The fragrance retention test shows that 9-hydroxy-2, 7-dimethyl octyl-2-butyrate presents strong bergamot fragrance, and the fragrance retention time is 52 hours.

Example 6

The embodiment provides an ester compound and a preparation method thereof, and the preparation method specifically comprises the following steps:

s1: 1422g of 2, 5-dimethyl-6-hepten-2-ol, 2373g of butyric anhydride and 3L of toluene are sequentially added into a 20L reaction kettle, and after uniform stirring, the temperature is raised to 110 ℃ for reaction for 4 hours. Under the pressure of 400Pa, the fraction with the vapor temperature of 104 ℃ and 106 ℃ is collected to obtain 1977g of 2, 5-dimethyl-6-heptene-2-butyrate.

S2: 212.3g of 2, 5-dimethyl-6-heptene-2-butanoic acid ester, 200mL of dried tetrahydrofuran, and 500mL of a 1mol/L tetrahydrofuran solution of diborane were added dropwise in this order to a 5L reaction vessel, and the reaction was carried out at room temperature for 2 hours. Then, while maintaining the temperature at room temperature, 650mL of a 1mol/L aqueous solution of sodium hydroxide was added, followed by dropwise addition of 112mL of a 9.79mol/L aqueous solution of hydrogen peroxide, and the reaction was carried out at room temperature for 1 hour. The mother liquor was concentrated, filtered to remove the residue, the mother liquor was distilled under 350Pa, and the fraction of the mother liquor at temperature of 122-126 ℃ was collected to obtain 202.1g of 7-hydroxy-2, 5-dimethylheptyl-2-butanoate.

The data of mass spectrometry for the gas chromatographic detection of 7-hydroxy-2, 5-dimethylheptyl-2-butyrate are as follows:

MS(ESI,m/z)253.3(M+Na⁺) (ii) a The theoretical calculation data of the high-resolution electrospray ionization mass spectrum is [ C ]₁₃H₂₆NaO₃]⁺(M+Na⁺)253.3330, the actual measured value was 253.3318.

And performing effect verification experiments including fragrance evaluation and fragrance retention test.

The fragrance evaluation of the compound was carried out by 5 perfumers who worked for more than 5 years:

fragrance retention test: 1 strip of fragrance-smelling test paper is dipped with 1g of 7-hydroxy-2, 5-dimethylheptyl-2-butyrate. The test paper is placed on a fragrance smelling frame, 5 fragrance regulating operators smell the test paper once every 2 hours, and when the fragrance of the fragrance smelling test paper cannot be sensed by more than or equal to 2 fragrance regulating operators, the fragrance remaining time is recorded.

The fragrance retention test shows that the 7-hydroxy-2, 5-dimethylheptyl-2-butyrate presents obvious bergamot fragrance, and the fragrance retention time is 48 hours.

Example 7

The embodiment provides an ester compound and a preparation method thereof, and the preparation method specifically comprises the following steps:

s1: 1282g of 2, 4-dimethyl-5-hexene-2-ol, 2373g of butyric anhydride and 3L of toluene are sequentially added into a 20L reaction kettle, stirred uniformly, heated to 110 ℃ and reacted for 4 hours. Under the pressure of 400Pa, the fraction with the vapor temperature of 101 ℃ and 103 ℃ is collected to obtain 1766g of 2, 4-dimethyl-5-hexene-2-butyrate.

S2: 198.3g of 2, 4-dimethyl-5-hexene-2-butyrate, 200mL of dried tetrahydrofuran, and 500mL of a 1mol/L tetrahydrofuran solution of diborane were added dropwise in this order to a 5L reactor, and the reaction was carried out at room temperature for 2 hours. Then, while maintaining the temperature at room temperature, 650mL of a 1mol/L aqueous solution of sodium hydroxide was added, followed by dropwise addition of 112mL of a 9.79mol/L aqueous solution of hydrogen peroxide, and the reaction was carried out at room temperature for 1 hour. The mother liquor was concentrated, filtered to remove the residue, the mother liquor was distilled under 350Pa, and the fraction of 6-hydroxy-2, 4-dimethylhexyl-2-butyrate 189.1g, which was the mother liquor at 118-122 ℃ was collected.

Mass spectrometry data for 6-hydroxy-2, 4-dimethylhexyl-2-butyrate were as follows:

MS(ESI,m/z)239.3(M+Na⁺) (ii) a The theoretical calculation data of the high-resolution electrospray ionization mass spectrum is [ C ]₁₂H₂₄NaO₃]⁺(M+Na⁺)239.3064, the actual measured value was 239.3052.

And performing effect verification experiments including fragrance evaluation and fragrance retention test.

The fragrance evaluation of the compound was carried out by 5 perfumers who worked for more than 5 years:

fragrance retention test: 1 strip of fragrance-smelling test paper is dipped with 1g of 6-hydroxy-2, 4-dimethylhexyl-2-butyrate. The test paper is placed on a fragrance smelling frame, 5 fragrance regulating operators smell the test paper once every 2 hours, and when the fragrance of the fragrance smelling test paper cannot be sensed by more than or equal to 2 fragrance regulating operators, the fragrance remaining time is recorded.

The fragrance retention test shows that the 6-hydroxy-2, 4-dimethyl hexyl-2-butyrate presents strong mixed fragrance of bergamot, lemon and green grass fragrance, and the fragrance retention time is 44 hours.

Comparative example 1

For the 2, 6-dimethyl-7-octene-2-butanoic acid ester obtained in example 1The fragrance evaluation was carried out, and the fragrance of the compound was evaluated by 5 perfumers who worked for 5 years or more as follows:

and (3) fragrance testing: 1 strip of fragrance-smelling test paper is dipped with 1g of 2, 6-dimethyl-7-octene-2-butyrate. The test paper was placed on a fragrance-smelling stand and smelled by a 5-position fragrance mixer every 2 hours and the fragrance characteristics were recorded. When more than or equal to 2 blending operators can not sense the aroma of the aroma smelling test paper, the aroma remaining time is recorded.

The aroma test shows that the aroma of the 2, 6-dimethyl-7-octene-2-butyrate is slightly pineapple-like tropical fruit aroma, the characteristic aroma of bergamot is not possessed, and the aroma retention time is 28 hours.

Comparative example 2

P-7-hydroxy-2, 6-dimethyloctyl-2-butyrateThe fragrance evaluation was carried out, and the fragrance of the compound was evaluated by 5 perfumers who worked for 5 years or more as follows:

and (3) fragrance testing: 1 strip of fragrance-smelling test paper is dipped with 1g of 7-hydroxy-2, 6-dimethyl octyl-2-butyrate. The test paper was placed on a fragrance-smelling stand and smelled by a 5-position fragrance mixer every 2 hours and the fragrance characteristics were recorded. When more than or equal to 2 blending operators can not sense the aroma of the aroma smelling test paper, the aroma remaining time is recorded.

The aroma test shows that the aroma of the 2, 6-dimethyl-7-octene-2-butyrate is jasmine aroma and ester wax aroma, the bergamot characteristic aroma is not possessed, and the aroma retention time is 36 hours.

The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.

The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.