CN111285756B - Synthetic method of perfume megastigmatrienone intermediate 3-oxo-alpha-ionol - Google Patents
Synthetic method of perfume megastigmatrienone intermediate 3-oxo-alpha-ionol Download PDFInfo
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
- C07C49/587—Unsaturated compounds containing a keto groups being part of a ring
- C07C49/703—Unsaturated compounds containing a keto groups being part of a ring containing hydroxy groups
- C07C49/743—Unsaturated compounds containing a keto groups being part of a ring containing hydroxy groups having unsaturation outside the rings, e.g. humulones, lupulones
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/16—Systems containing only non-condensed rings with a six-membered ring the ring being unsaturated
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Abstract
The invention discloses a method for synthesizing a perfume megastigmatrienone intermediate 3-oxo-alpha-ionol, which relates to the technical field of perfume synthesis and comprises the following steps: (1) synthesizing 3-oxo-alpha-ionone; (2) synthesis of 3-oxo-alpha-ionol. The invention takes alpha-ionone as a reaction raw material, and prepares the 3-oxo-alpha-ionol through oxidation reaction and reduction reaction, the reaction condition is mild, and the reaction operation and the post-treatment are simple and convenient; and the total yield of the product 3-oxo-alpha-ionol reaches more than 80 percent, and the purity reaches more than 99 percent, so that the product 3-oxo-alpha-ionol can be used as a high-quality intermediate for synthesizing the flavor megastigmatrienone.
Description
The technical field is as follows:
the invention relates to the technical field of perfume synthesis, and particularly relates to a synthesis method of perfume megastigmatrienone intermediate 3-oxo-alpha-ionol.
Background art:
megastigmatrienone is oily liquid, has tobacco fragrance and spicy bottom, can enhance the tobacco fragrance, improve the smoking taste, harmonize the smoke and reduce the irritation, is an indispensable spice for preparing various high-grade cigarettes, and has important application in the tobacco industry.
The 3-oxo-alpha-ionol belongs to an important intermediate for synthesizing megastigmatrienone, so that the improvement of the yield and the purity of the 3-oxo-alpha-ionol is beneficial to improving the quality of the intermediate used for synthesizing megastigmatrienone, and further improving the yield of the megastigmatrienone.
At present, alpha-ionone is usually used as a starting material for synthesizing 3-oxo-alpha-ionol, and the 3-oxo-alpha-ionol is prepared through oxidation reaction and reduction reaction, but the yield of the existing synthesis process is very low. The invention synthesizes and obtains the 3-oxo-alpha-ionol with high yield and high purity by improving the prior synthesis process.
The invention content is as follows:
the technical problem to be solved by the invention is to provide a synthesis method of a flavor megastigmatrienone intermediate 3-oxo-alpha-ionol, wherein the total yield of the 3-oxo-alpha-ionol is improved to more than 80% and the purity is improved to more than 99% by improving process conditions.
The technical problem to be solved by the invention is realized by adopting the following technical scheme:
the synthesis method of the perfume megastigmatrienone intermediate 3-oxo-alpha-ionol comprises the following steps:
(1) Synthesis of 3-oxo- α -ionone: adding alpha-ionone and an oxidant into acetone under the protection of nitrogen, heating for reaction, filtering after the reaction is finished, distilling and recovering the acetone, extracting distillation residues with anhydrous ether, and distilling and recovering the ether from the obtained ether layer to obtain an oily substance;
(2) Synthesis of 3-oxo- α -ionol: dissolving the obtained oily substance in absolute ethyl alcohol, adding sodium borohydride, reacting at normal temperature, adding acetone to decompose unreacted sodium borohydride after the reaction is finished, adding water to dilute, extracting with absolute ethyl ether, washing with water, drying, distilling to recover ethyl ether, and recrystallizing with absolute ethyl alcohol to obtain the product.
The mol ratio of the alpha-ionone to the oxidant is 1.
The reaction temperature of the heating reaction is 45-55 ℃.
The oxidant is vanadium cyclopentadienyl.
The oxidant is yttrium (III) trifluoroacetate hydrate.
Chromium sesquioxide or chromate is commonly used as an oxidizing agent in the art, but the yield of 3-oxo-alpha-ionone is low. This is because 3-oxo- α -ionone and 4-oxo- α -ionone can be produced by oxidation of α -ionone, and it is necessary to increase the selectivity of the oxidation reaction in order to obtain 3-oxo- α -ionone in high yield. Therefore, the invention adopts the cyclopentadienyl vanadium or the yttrium (III) trifluoroacetate hydrate as the oxidant, and improves the yield of the 3-oxo-alpha-ionone to more than 90 percent, thereby realizing the new application of the cyclopentadienyl vanadium or the yttrium (III) trifluoroacetate hydrate as the allylic oxidant.
The mol ratio of the alpha-ionone to the sodium borohydride is 1.1-0.5.
The adding temperature of the sodium borohydride is controlled to be 7-12 ℃.
In order to improve the yield of the 3-oxo-alpha-ionol, the invention also adds a catalyst in the reduction reaction, and the catalyst is matched with sodium borohydride to promote the efficient operation of the reduction reaction, namely, the technical problem to be solved by the invention can be realized by adopting the following technical scheme:
the synthesis method of the perfume megastigmatrienone intermediate 3-oxo-alpha-ionol comprises the following steps:
(1) Synthesis of 3-oxo- α -ionone: adding alpha-ionone and an oxidant into acetone under the protection of nitrogen, heating for reaction, filtering after the reaction is finished, distilling and recovering the acetone, extracting distillation residues with anhydrous ether, and distilling and recovering the ether from the obtained ether layer to obtain an oily substance;
(2) Synthesis of 3-oxo- α -ionol: dissolving the obtained oily substance in absolute ethyl alcohol, adding sodium borohydride and a catalyst, reacting at normal temperature, filtering after the reaction is finished, adding acetone into filtrate to decompose unreacted sodium borohydride, adding water to dilute, extracting with absolute ethyl ether, washing with water, drying, distilling to recover ethyl ether, and recrystallizing with absolute ethyl alcohol to obtain the product.
The mol ratio of the alpha-ionone to the oxidant is 1.05-0.5.
The reaction temperature of the heating reaction is 45-55 ℃.
The oxidant is vanadium cyclopentadienyl.
The oxidant is yttrium (III) trifluoroacetate hydrate.
The mol ratio of the alpha-ionone to the sodium borohydride to the catalyst is 1.1-0.5.
The adding temperature of the sodium borohydride is controlled to be 7-12 ℃.
The catalyst is molybdenum acetylacetonate.
While oxymolybdenum acetylacetonate is commonly used in the art as a catalyst for domino reactions, the inventors have unexpectedly discovered during the course of their experiments that the addition of oxymolybdenum acetylacetonate results in a significant increase in the yield of the product 3-oxo- α -ionol upon such reduction.
The invention has the beneficial effects that: the invention takes alpha-ionone as a reaction raw material, and prepares the 3-oxo-alpha-ionol through oxidation reaction and reduction reaction, the reaction condition is mild, and the reaction operation and the post treatment are simple and convenient; and the total yield of the product 3-oxo-alpha-ionol reaches more than 80 percent, and the purity reaches more than 99 percent, so that the product 3-oxo-alpha-ionol can be used as a high-quality intermediate for synthesizing the flavor megastigmatrienone.
The specific implementation mode is as follows:
in order to make the technical means, the creation characteristics, the achievement purposes and the effects of the invention easy to understand, the invention is further described with the specific embodiments.
Example 1
(1) Synthesis of 3-oxo- α -ionone: under the protection of nitrogen, adding 20mmol of alpha-ionone and 5mmol of cyclopentadienyl vanadium into 50mL of acetone, heating to 55 ℃, keeping the temperature and reacting for 3 hours, filtering after the reaction is finished, distilling and recovering the acetone, extracting distillation residues with 50mL of anhydrous ether, distilling the obtained ether layer and recovering the ether to obtain oily substances;
(2) Synthesis of 3-oxo-alpha-ionol: the oily substance obtained above is dissolved in 50mL of absolute ethyl alcohol, and 8mmol of sodium borohydride is added at 10 DEG CAnd keeping the temperature at 25 ℃ for reaction for 4 hours, adding 5mL of acetone to decompose unreacted sodium borohydride after the reaction is finished, adding 25mL of water to dilute the sodium borohydride, extracting the sodium borohydride by using 50mL of anhydrous ether, washing the sodium borohydride by using 25mL of water, drying the sodium borohydride by using 5g of anhydrous magnesium sulfate, distilling and recovering ether, and recrystallizing the ether by using 25mL of anhydrous ethanol to obtain the product, wherein the total yield is 83.7 percent, and the purity is 99.4 percent. ESI-MS: m/z =209.15[ 2 ], [ M +1 ]] + 。
Example 2
Example 2 differs from example 1 in that the oxidant, vanadyl, was replaced by yttrium (III) trifluoroacetate hydrate and is otherwise identical to example 1.
(1) Synthesis of 3-oxo-alpha-ionone: under the protection of nitrogen, adding 20mmol of alpha-ionone and 5mmol of yttrium (III) trifluoroacetate hydrate into 50mL of acetone, heating to 55 ℃, preserving the temperature, reacting for 3 hours, filtering after the reaction is finished, distilling and recovering the acetone, extracting the distillation residue with 50mL of anhydrous ether, distilling the obtained ether layer and recovering the ether to obtain an oily substance;
(2) Synthesis of 3-oxo- α -ionol: dissolving the obtained oily matter in 50mL of absolute ethyl alcohol, adding 8mmol of sodium borohydride at 10 ℃, keeping the temperature at 25 ℃ for reaction for 4 hours, adding 5mL of acetone to decompose unreacted sodium borohydride after the reaction is finished, adding 25mL of water for dilution, then extracting with 50mL of anhydrous ether, washing with 25mL of water, drying with 5g of anhydrous magnesium sulfate, distilling and recovering ether, and recrystallizing with 25mL of absolute ethyl alcohol to obtain the product, wherein the total yield is 84.9%, and the purity is 99.5%.
Example 3
Example 3 differs from example 1 in that the catalyst molybdenum acetylacetonate is added with sodium borohydride, and is otherwise identical to example 1.
(1) Synthesis of 3-oxo- α -ionone: under the protection of nitrogen, adding 20mmol of alpha-ionone and 5mmol of vanadyl into 50mL of acetone, heating to 55 ℃, keeping the temperature and reacting for 3 hours, filtering after the reaction is finished, distilling and recovering acetone, extracting distillation residues by using 50mL of anhydrous ether, distilling the obtained ether layer and recovering ether to obtain oily matter;
(2) Synthesis of 3-oxo- α -ionol: dissolving the obtained oily matter in 50mL of absolute ethyl alcohol, adding 8mmol of sodium borohydride and 1mmol of acetylacetonato-molybdenum oxide at 10 ℃, preserving the temperature at 25 ℃ for 4 hours of reaction, filtering after the reaction is finished, adding acetone into filtrate to decompose unreacted sodium borohydride, adding 25mL of water for dilution, then extracting with 50mL of anhydrous ether, washing with 25mL of water, drying with 5g of anhydrous magnesium sulfate, distilling and recovering ether, and recrystallizing with 25mL of absolute ethyl alcohol to obtain the product, wherein the total yield is 88.4%, and the purity is 99.5%.
Comparative example 1
Comparative example 1 differs from example 1 in that the oxidizing agent vanadyl is replaced by chromium sesquioxide and is otherwise identical to example 1.
(1) Synthesis of 3-oxo- α -ionone: under the protection of nitrogen, adding 20mmol of alpha-ionone and 5mmol of chromium trioxide into 50mL of acetone, heating to 55 ℃, carrying out heat preservation reaction for 3 hours, filtering after the reaction is finished, distilling and recovering acetone, extracting distillation residues by using 50mL of anhydrous ether, distilling the obtained ether layer and recovering ether to obtain oily matter;
(2) Synthesis of 3-oxo- α -ionol: dissolving the oily substance prepared in the previous step in 50mL of absolute ethyl alcohol, adding 8mmol of sodium borohydride at 10 ℃, keeping the temperature at 25 ℃ for reaction for 4 hours, adding 5mL of acetone to decompose unreacted sodium borohydride after the reaction is finished, adding 25mL of water for dilution, extracting with 50mL of anhydrous ether, washing with 25mL of water, drying with 5g of anhydrous magnesium sulfate, distilling and recovering ether, and recrystallizing with 25mL of absolute ethyl alcohol to obtain the product, wherein the total yield is 62.5%, and the purity is 99.1%.
Comparative example 2
Comparative example 2 is different from example 1 in that the oxidizing agent metallocenium is replaced with pyridinium chlorochromate and the rest is identical to example 1.
(1) Synthesis of 3-oxo- α -ionone: under the protection of nitrogen, adding 20mmol of alpha-ionone and 5mmol of pyridinium chlorochromate into 50mL of acetone, heating to 55 ℃, keeping the temperature and reacting for 3 hours, filtering after the reaction is finished, distilling and recovering acetone, extracting distillation residues with 50mL of anhydrous ether, distilling and recovering ether from an obtained ether layer to obtain an oily substance;
(2) Synthesis of 3-oxo- α -ionol: dissolving the oily substance prepared in the previous step in 50mL of absolute ethyl alcohol, adding 8mmol of sodium borohydride at 10 ℃, keeping the temperature at 25 ℃ for reaction for 4 hours, adding 5mL of acetone to decompose unreacted sodium borohydride after the reaction is finished, adding 25mL of water for dilution, extracting with 50mL of anhydrous ether, washing with 25mL of water, drying with 5g of anhydrous magnesium sulfate, distilling and recovering ether, and recrystallizing with 25mL of absolute ethyl alcohol to obtain the product, wherein the total yield is 67.3%, and the purity is 99.2%.
The foregoing shows and describes the general principles and broad features of the present invention and advantages thereof. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (5)
1. The synthesis method of the perfume megastigmatrienone intermediate 3-oxo-alpha-ionol is characterized by comprising the following steps of:
(1) Synthesis of 3-oxo- α -ionone: adding alpha-ionone and an oxidant into acetone under the protection of nitrogen, heating for reaction, filtering after the reaction is finished, distilling and recovering the acetone, extracting distillation residues by using anhydrous ether, and distilling and recovering the ether from an obtained ether layer to obtain an oily substance;
(2) Synthesis of 3-oxo- α -ionol: dissolving the obtained oily substance in absolute ethyl alcohol, adding sodium borohydride, reacting at normal temperature, adding acetone to decompose unreacted sodium borohydride after the reaction is finished, adding water to dilute, extracting with absolute ethyl ether, washing with water, drying, distilling to recover ethyl ether, and recrystallizing with absolute ethyl alcohol to obtain a product;
the oxidant is vanadium dicyclopentadienyl or yttrium (III) trifluoroacetate hydrate.
2. The method of synthesis according to claim 1, characterized in that: the mol ratio of the alpha-ionone to the oxidant is 1.05-0.5.
3. The method of synthesis according to claim 1, characterized in that: the reaction temperature of the heating reaction is 45-55 ℃.
4. The method of synthesis according to claim 1, characterized in that: the mol ratio of the alpha-ionone to the sodium borohydride is 1.1-0.5.
5. The method of synthesis according to claim 1, characterized in that: the adding temperature of the sodium borohydride is controlled to be 7-12 ℃.
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| CN102140484A (en) * | 2010-12-16 | 2011-08-03 | 郑州奥利实业有限公司 | Synthesis method of 3-oxo-alpha-ionol esters |
| WO2019109045A1 (en) * | 2017-12-01 | 2019-06-06 | The Scripps Research Institute | Direct oxidative amination of hydrocarbons |
| CN110407178A (en) * | 2018-04-27 | 2019-11-05 | 程贤阳 | A kind of Metal Substrate liquid oxidizer and preparation method thereof |
| CN110590522A (en) * | 2019-10-12 | 2019-12-20 | 广州百花香料股份有限公司 | Synthesis method of megastigmatrienone |
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Patent Citations (4)
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| CN102140484A (en) * | 2010-12-16 | 2011-08-03 | 郑州奥利实业有限公司 | Synthesis method of 3-oxo-alpha-ionol esters |
| WO2019109045A1 (en) * | 2017-12-01 | 2019-06-06 | The Scripps Research Institute | Direct oxidative amination of hydrocarbons |
| CN110407178A (en) * | 2018-04-27 | 2019-11-05 | 程贤阳 | A kind of Metal Substrate liquid oxidizer and preparation method thereof |
| CN110590522A (en) * | 2019-10-12 | 2019-12-20 | 广州百花香料股份有限公司 | Synthesis method of megastigmatrienone |
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