Beta-alkoxy ketone with lasting fragrance, and preparation method and application thereof

Abstract

The invention belongs to the technical field of organic synthesis, and particularly relates to beta-alkoxy ketone with lasting fragrance retention as well as a preparation method and application of the beta-alkoxy ketone. The invention provides a preparation method of beta-alkoxy ketone with lasting fragrance, which comprises the following steps: mixing alpha, beta-unsaturated ketone and an alcohol compound, and carrying out Michael addition reaction in the presence of an acid catalyst to obtain the beta-alkoxy ketone, the acid catalyst comprises one or more of bis (trifluoromethanesulfonimide), sodium p-toluenesulfinate, tricyclohexylphosphine and tetramethylguanidine. The beta-alkoxy ketone is synthesized by starting from an alcohol raw material which is cheaper and easier to obtain, the method which is simple to operate and mild in condition is provided, and since the leaving ability of alkoxy is smaller than that of sulfydryl, the beta-alkoxy ketone can release alpha, beta-unsaturated ketone more slowly, so that the purpose of lasting fragrance is achieved.

Description

Technical Field

[0001] The present invention belongs to the technical field of organic synthesis, and particularly relates to a β-alkoxy ketone with long-lasting fragrance retention, and a preparation method and application thereof. Background Art

[0002] α,β-unsaturated ketone is a kind of perfume molecule, which is widely used in daily life. However, due to its strong volatility, it is very difficult to make the fragrance last for a long time. How to improve the stability and slow-release property of the perfume to enhance the fragrance retention duration has become the key point in the development of perfumes.

[0003] The traditional method is to convert α,β-unsaturated ketone into β-mercapto ketone to achieve the purpose of slow release. However, the above conversion requires the use of sulfur reagents with a strong smell, which usually cause irritation to people during use, and the release rate of β-mercapto ketone to α,β-unsaturated ketone is very fast, resulting in poor fragrance retention duration. Summary of the Invention

[0004] The purpose of the present invention is to provide a β-alkoxy ketone with long-lasting fragrance retention, and a preparation method and application thereof. The β-alkoxy ketone obtained by the method provided by the present invention can slowly release α,β-unsaturated ketone so as to achieve the purpose of long-lasting fragrance retention.

[0005] To achieve the above purpose, the present invention provides the following technical solutions:

[0006] The present invention provides a preparation method of a β-alkoxy ketone with long-lasting fragrance retention, comprising the following steps:

[0007] Mix an α,β-unsaturated ketone and an alcohol compound, and carry out a Michael addition reaction in the presence of an acid catalyst to obtain the β-alkoxy ketone;

[0008] The acid catalyst includes one or more of bis(trifluoromethanesulfonyl)imide, sodium p-toluenesulfinate, tricyclohexylphosphine, and tetramethylguanidine.

[0009] Preferably, the α,β-unsaturated ketone has the structure shown in Formula I;

[0010]

[0011] R includes an alkyl group, an aryl group, an amino group, or a hydroxyl group.

[0012] Preferably, the alcohol compound has the structure shown in Formula II: R 1 -OH Formula II;

[0013] R 1 includes an alkyl group, a substituted alkyl group, an aryl group, or a benzyl group;

[0014] The alkyl group includes dodecyl, methyl or ethyl; the substituted alkyl group includes trifluoroethyl.

[0015] Preferably, the α,β-unsaturated ketone is delta-damascone; the alcohol compound is benzyl alcohol, lauryl alcohol or trifluoroethanol.

[0016] Preferably, the molar ratio of the α,β-unsaturated ketone to the alcohol compound is 1:1 to 1:3.

[0017] Preferably, the molar amount of the catalyst is 0.5 to 10% of the molar amount of the α,β-unsaturated ketone.

[0018] Preferably, the temperature of the Michael addition reaction is room temperature and the time is 2 to 120 h.

[0019] Preferably, after the Michael addition reaction, the obtained product is purified by column chromatography.

[0020] The present invention also provides a β-alkoxy ketone with long-lasting fragrance prepared by the preparation method described in the above technical solution.

[0021] The present invention also provides the application of the β-alkoxy ketone with long-lasting fragrance described in the above technical solution as a fragrance.

[0022] The present invention provides a preparation method of a β-alkoxy ketone with long-lasting fragrance, comprising the following steps: mixing an α,β-unsaturated ketone and an alcohol compound, and carrying out a Michael addition reaction in the presence of an acid catalyst to obtain the β-alkoxy ketone; the acid catalyst includes one or more of bis(trifluoromethanesulfonyl)imide, sodium p-toluenesulfinate, tricyclohexylphosphine and tetramethylguanidine. Starting from more inexpensive and readily available alcohol raw materials, the present invention provides a method for synthesizing β-alkoxy ketone with simple operation and mild conditions. Since the leaving ability of the alkoxy group is less than that of the mercapto group, the β-alkoxy ketone can release the α,β-unsaturated ketone more slowly, thereby achieving the purpose of long-lasting fragrance.

[0023] In addition, the present invention does not require heating, low temperature or inert atmosphere, and can react under room temperature air conditions, and only requires a catalytic amount of acid. The method provided by the present invention can efficiently and highly selectively convert an alcohol and an α,β-unsaturated ketone into a β-alkoxy ketone. The raw materials are inexpensive and readily available, the operation is simple, and the reaction conditions are mild, which is suitable for industrial production. Description of the Drawings

[0024] Figure 1 1H NMR spectrum of target product 1;

[0025] Figure 2 GC-MS spectrum of target product 1;

[0026] Figure 3 1H NMR spectrum of target product 2;

[0027] Figure 4 GC-MS spectrum of target product 2;

[0028] Figure 5 GC-MS spectrum of target product 3;

[0029] Figure 6 Retention test result chart of the target product in Test Example 1. Detailed implementation mode

[0030] The present invention provides a method for preparing a β-alkoxy ketone with long-lasting fragrance retention, comprising the following steps:

[0031] Mix an α,β-unsaturated ketone and an alcohol compound, and carry out a Michael addition reaction in the presence of an acid catalyst to obtain the β-alkoxy ketone;

[0032] The acid catalyst includes one or more of bis(trifluoromethanesulfonyl)imide, sodium p-toluenesulfinate, tricyclohexylphosphine, and tetramethylguanidine.

[0033] In the present invention, the α,β-unsaturated ketone preferably has the structure shown in Formula I;

[0034]

[0035] R preferably includes an alkyl group, an aryl group, an amino group, or a hydroxyl group.

[0036] In the present invention, the α,β-unsaturated ketone is preferably δ-damascone.

[0037] In the present invention, the alcohol compound preferably has the structure shown in Formula II: R 1 -OH Formula II. In the present invention, the R 1 preferably includes an alkyl group, a substituted alkyl group, an aryl group, or a benzyl group; the alkyl group preferably includes a dodecyl group, a methyl group, or an ethyl group; the substituted alkyl group preferably includes a trifluoroethyl group. In the present invention, the alcohol compound is preferably benzyl alcohol, lauryl alcohol, or trifluoroethanol.

[0038] In the present invention, the molar ratio of the α,β-unsaturated ketone to the alcohol compound is preferably 1:1 to 1:3, and more preferably 1:2.

[0039] In the present invention, the acid catalyst includes one or more of bis(trifluoromethanesulfonyl)imide, sodium p-toluenesulfinate, tricyclohexylphosphine, and tetramethylguanidine. In the present invention, the molar amount of the catalyst is preferably 0.5 to 10% of the molar amount of the α,β-unsaturated ketone, and specifically may be 0.5%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%.

[0040] In the present invention, the temperature of the Michael addition reaction is preferably room temperature, and the time is preferably 2 to 120 h, and specifically may be 2 h, 12 h, 24 h, 48 h, 72 h, 96 h, 120 h. In the present invention, after the Michael addition reaction, it is further preferred to include purifying the obtained product by column chromatography. The present invention has no special limitation on the process of the column chromatography, and those well-known to those skilled in the art can be used.

[0041] The chemical reaction equation of the preparation method provided by the present invention is (where the catalyst is bis(trifluoromethanesulfonyl)imide):

[0042]

[0043] The present invention also provides a β-alkoxy ketone with long-lasting fragrance prepared by the preparation method described in the above technical solution.

[0044] In the present invention, the β-alkoxy ketone preferably has the structure shown in Formula III:

[0045]

[0046] The R preferably includes alkyl, aryl, amino, or hydroxyl;

[0047] The R 1 preferably includes alkyl, substituted alkyl, aryl, or benzyl; the alkyl preferably includes dodecyl, methyl, or ethyl; the substituted alkyl preferably includes trifluoroethyl.

[0048] The present invention also provides the application of the β-alkoxy ketone with long-lasting fragrance described in the above technical solution as a fragrance.

[0049] Unless otherwise specified, the materials and equipment used in the present invention are all commercially available products in the art.

[0050] Next, the technical solutions in the present invention will be clearly and completely described in conjunction with the examples in the present invention. Obviously, the described examples are only a part of the examples of the present invention, rather than all the examples. Based on the examples in the present invention, all other examples obtained by those of ordinary skill in the art without creative efforts shall fall within the protection scope of the present invention.

[0051] Example 1

[0052] Benzyl alcohol (1.55 mL, 15 mmol) and δ-damascone (5.0 mmol) were mixed, and bis(trifluoromethanesulfonyl)imide (10 mol% of the molar amount of δ-damascone) was used as a catalyst. The reaction was carried out at room temperature for 24 hours, and then the target product 1 was obtained by column chromatography purification;

[0053] The chemical reaction equation is:

[0054]

[0055] Figure 1 is the 1H NMR spectrum of the target product 1, Figure 2 is the GC-MS spectrum of the target product 1;

[0056] From Figure 1 and Figure 2 it can be confirmed that the target product 1 was successfully prepared by the above process.

[0057] Example 2

[0058] Lauryl alcohol (3.36 mL, 15 mmol) and δ-damascone (5.0 mmol) were mixed, and bis(trifluoromethanesulfonyl)imide (10 mol% of the molar amount of δ-damascone) was used as a catalyst. The reaction was carried out at room temperature for 24 hours, and then the target product 2 was obtained by column chromatography purification;

[0059] The chemical reaction equation is:

[0060]

[0061] Figure 3 is the 1H NMR spectrum of the target product 2, Figure 4 is the GC-MS spectrum of the target product 2;

[0062] From Figure 3 and Figure 4 it can be confirmed that the target product 2 was successfully prepared by the above process.

[0063] Example 3

[0064] Trifluoroethanol (1.08 mL, 15 mmol) and δ-damascone (5.0 mmol) were mixed, and bis(trifluoromethanesulfonyl)imide (10 mol% of the molar amount of δ-damascone) was used as a catalyst. The reaction was carried out at room temperature for 24 hours, and then the target product 3 was obtained by column chromatography purification;

[0065] The chemical reaction equation is:

[0066]

[0067] Figure 5It is the GC-MS chart of the target product 3;

[0068] From Figure 5 It can be confirmed that the above process successfully prepared the target product 3.

[0069] Performance test

[0070] Using the target products obtained in Examples 1 to 2 as fragrance samples (where the target product 1 obtained in Example 1 corresponds to Compound 3, and the target product 2 obtained in Example 2 corresponds to Compound 5), the fragrance retention effect was tested;

[0071] Test method:

[0072] Add the fragrance sample in an amount of 1 mmol to 80 g of a fragrance-free laundry detergent matrix. After vigorous stirring and mixing, pour the mixture into a "Midea MB55V35E" household washing machine filled with 60 L of tap water, and wash 40 small towels (30*30 cm, about 40 g each) under standard program at room temperature. After the washing is completed, the 40 small towels are dried in a drying room for 24 h. Randomly select 18 small towels, then loosely package them in aluminum foil, and conduct aroma evaluation at 24 h, 72 h, 120 h, and 168 h.

[0073] The number of evaluators is 18, and the tested towels are scored according to the intensity level from 1 to 7 (1: no smell, 2: faint smell, 3: slightly weak smell, 4: medium smell, 5: slightly strong smell, 6: strong smell, 7: very strong smell).

[0074] Using delta-Damascone (corresponding to Compound 1) as a comparative sample, the same test was conducted, and the test results are shown in Table 1 and Figure 6 as follows;

[0075] Table 1 Fragrance retention effect of the target products obtained in the examples

[0076]

[0077]

[0078] From Table 1 and Figure 6 it can be seen that the average score of the odor intensity measured for Compound 3 and Compound 5 at each time point is higher than that of Compound 1; the average score of the odor intensity of Compound 1 at 120 h is "1" (no smell), while Compounds 3 and 5 still have aroma at 168 h, indicating that Compounds 3 and 5 can release α,β-unsaturated ketones more slowly to achieve the purpose of long-lasting fragrance retention.

[0079] Although the above embodiments have described the present invention in detail, they are only a part of the embodiments of the present invention, rather than all embodiments. Other embodiments can also be obtained based on these embodiments without creative efforts, and these embodiments all fall within the protection scope of the present invention.

Claims

1. A method for preparing a β-alkoxy ketone with a long-lasting fragrance, characterized in that: The following steps are involved: The α,β-unsaturated ketone and the alcohol compound are mixed, and Michael addition reaction is carried out in the presence of an acid catalyst to obtain the β-alkoxy ketone; The acid catalyst includes one or more of bistrifluoromethanesulfonyl imide, sodium p-toluenesulfinate, tricyclohexylphosphine and tetramethylguanidine.

2. The preparation method according to claim 1, characterized in that: The α,β-unsaturated ketone has a structure shown in Formula I; The R includes an alkyl group, an aryl group, an amino group or a hydroxyl group.

3. The preparation method according to claim 1, characterized in that: The alcohol compound has a structure shown in Formula II: 1 -OH formula II; The R 1 including alkyl, substituted alkyl, aryl or benzyl; The alkyl group includes dodecyl, methyl or ethyl; and the substituted alkyl group includes trifluoroethyl.

4. The preparation method according to claim 1, characterized in that: The α,β-unsaturated ketone is butyl-damascenone; and the alcohol compound is benzyl alcohol, lauryl alcohol or trifluoroethanol.

5. The preparation method according to any one of claims 1 to 4, characterized in that: The molar ratio of the α,β-unsaturated ketone to the alcohol compound is 1:1 to 1:

3.

6. The preparation method according to claim 5, characterized in that: The molar amount of the catalyst is 0.5-10% of the molar amount of the α,β-unsaturated ketone.

7. The preparation method according to claim 1, characterized in that: The temperature of the Michael addition reaction is room temperature, and the time is 2 to 120 hours.

8. The preparation method according to claim 1, characterized in that: After the Michael addition reaction, the obtained product is purified by column chromatography.

9. The β-alkoxy ketone with long-lasting fragrance obtained by the preparation method according to any one of claims 1 to 8.

10. Use of the long-lasting and fragrant β-alkoxy ketone according to claim 9 as a perfume.

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