CN110922324A - Preparation method of 5(6) -decenoic acid - Google Patents
Preparation method of 5(6) -decenoic acid Download PDFInfo
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- CN110922324A CN110922324A CN201911015120.8A CN201911015120A CN110922324A CN 110922324 A CN110922324 A CN 110922324A CN 201911015120 A CN201911015120 A CN 201911015120A CN 110922324 A CN110922324 A CN 110922324A
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- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
- C07C51/353—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by isomerisation; by change of size of the carbon skeleton
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Abstract
The invention provides a preparation method of 5(6) -decenoic acid, which is characterized in that 2-butylcyclohexanone is subjected to carbamide oxidation and isomerization to synthesize the 5(6) -decenoic acid in one step. The preparation method of 5(6) -decenoic acid shortens the reaction route for industrially synthesizing 5(6) -decenoic acid, does not use strong acid catalysts, greatly reduces the discharge of three wastes, has small environmental protection pressure, avoids the corrosion of strong acid on equipment, and can greatly reduce the production cost, and compared with the traditional oxidation process, the preparation method of 5(6) -decenoic acid produced by the process uses percarbamide to replace hydrogen peroxide, has mild reaction, reduces side reactions, and is higher in safety, and the 5(6) -decenoic acid produced by the process is suitable for preparing essence of types such as cream, dairy, yoghourt, strawberry and the like.
Description
Technical Field
The invention relates to the technical field of perfume synthesis, in particular to a preparation method of 5(6) -decenoic acid.
Background
5(6) -decenoic acid, also known as milk lactone, CAS number 72881-27-7, FEMA number 3742, and is also recorded by GB2760, has strong milk fragrance and lasting fragrance, and is an important raw material of milk, cream and cheese essence. 5(6) -decenoic acid, because of its very high boiling point, is also used in baked goods and because it is not as easily destroyed as the compounded milk flavor, it has wide application in the flavor and fragrance cosmetic industry.
Due to the wide application range and the large market demand, the research on the synthesis of 5(6) -decenoic acid is reported frequently. In the existing reports, the mainstream production process route is that cyclohexanone and n-butyl aldehyde are used as raw materials, and the raw materials are subjected to aldol condensation, selective hydrogenation, hydrogen peroxide oxidation and ring expansion under the alkaline condition, and finally ring opening is carried out under the condition of sulfuric acid or phosphoric acid to obtain 5- (6) -decenoic acid. The whole synthesis route is long, hydrogen peroxide is directly used for oxidation ring expansion, the reaction heat release is severe, the temperature is not easy to control, the requirement on a refrigerating unit of equipment is high, and the safety coefficient is low. In addition, the 5(6) -decenoic acid is prepared by ring opening under an acidic condition, a large amount of acidic wastewater is generated and cannot be recycled, the environmental protection pressure is high, the corrosion of equipment caused by the use of strong acid is high, and the production cost is high.
Chinese patent "a new technology for preparing decenoic acid" (CN1426992A) provides a new technology for preparing 5(6) -decenoic acid, which adopts peroxyacetic acid as an oxidant in one step of oxidation and ring expansion, and finally uses clay treated by phosphoric acid as a catalyst to obtain the 5(6) -decenoic acid. The synthesis method still has the problems of long synthesis route, violent oxidation reaction heat release, large unsafe factors in the use of the peroxyacetic acid and the like. In addition, although clay is used as a carrier of phosphoric acid, a large amount of acid water can be avoided, but a large amount of solid waste is still generated.
Chinese patent '5 (6) -decenoic acid synthesis' (CN1597655A) provides a synthesis method for preparing a 5(6) -decenoic acid key intermediate 2-butylcyclohexanone, and the method adopts direct condensation and hydrogenation of cyclohexanone and n-butyl aldehyde under the action of a heterogeneous bifunctional catalyst palladium/aluminum oxide to realize the preparation of the 2-butylcyclohexanone in one step. The invention effectively shortens the synthetic route of the 5(6) -decenoic acid, but the invention still adopts the reaction steps of hydrogen peroxide oxidation ring expansion and ring opening under acidic condition to prepare the 5(6) -decenoic acid. Therefore, the problems of large safety factor and acidic waste water still exist in production, the environmental protection pressure is large, and the production cost is directly overhigh.
Therefore, the search for a simple and convenient 5(6) -decenoic acid production process with less three wastes to reduce the production cost becomes an urgent technical problem to be solved.
Disclosure of Invention
In view of the above, the present invention is directed to a method for preparing 5(6) -decenoic acid, which can provide a simple and convenient 5(6) -decenoic acid production process with less three wastes.
In order to achieve the purpose, the technical scheme of the invention is realized as follows:
a preparation method of 5(6) -decenoic acid is characterized in that 2-butylcyclohexanone is subjected to carbamide oxidation and isomerization to synthesize the 5(6) -decenoic acid in one step.
Further, the preparation method comprises the steps of adding formic acid into carbamide under ice-water bath to obtain a mixture, uniformly stirring, dropwise adding 2-butylcyclohexanone into the mixture, and continuously stirring for reaction after dropwise adding to obtain a reaction solution; then, adding water into the reaction liquid for quenching reaction and liquid separation, and mixing, extracting and separating the lower-layer water phase after liquid separation and cyclohexane to obtain an oil phase; then, the separated oil phase is washed to be neutral by water, and then is subjected to desolventizing and rectification, and the fraction with the temperature of 190-230 ℃ is collected to obtain the 5(6) -decenoic acid product.
Further, the percarbamide is added with formic acid with the concentration of 80-90% by weight, and the weight ratio of the percarbamide to the formic acid is 1: 1-3.
Further, the weight ratio of the mixture to the dropwise added 2-butylcyclohexanone is 1:0.1-0.2, and the dropwise addition rate of the 2-butylcyclohexanone should be controlled to maintain the temperature of the reaction solution at 25-40 ℃.
Further, after dropwise adding 2-butylcyclohexanone, continuously stirring for 0.5-3h to obtain a reaction solution.
Further, the weight ratio of the reaction liquid to water was 1: 1.5.
Further, the volume ratio of the lower aqueous phase to cyclohexane is 1: 0.2-1.0, and extracting the lower aqueous phase and cyclohexane under the same conditions for 1-3 times, wherein the oil phase obtained in each time is combined together.
Further, the volume ratio of the oil phase to the water is 1:2-4, and washing the oil phase and the water for 1-3 times according to the volume ratio of 1: 2-4.
Furthermore, the desolventizing is to remove the solvent contained in the washed oil phase under the heating condition, and the desolventized oil phase is rectified under the conditions of reduced pressure and heating to remove impurities contained in the oil phase.
Further, the 5(6) -decenoic acid product is obtained by collecting the fraction at 230 ℃ and 190 ℃ when the temperature in the distillation kettle reaches 260 ℃ and 220 ℃ during rectification, and the content of the 5(6) -decenoic acid in the obtained 5(6) -decenoic acid product is 85-95% by weight.
Compared with the prior art, the invention has the following advantages:
compared with the prior art, the preparation method shortens the production process route of the 5(6) -decenoic acid, avoids using a strong acid catalyst, can greatly reduce the discharge of three wastes, has small environmental protection pressure, can also avoid the corrosion of strong acid on equipment, and can greatly reduce the production cost.
In addition, compared with the traditional oxidation process, the preparation method of the invention uses the percarbamide as the oxidant to replace hydrogen peroxide, so that the reaction conditions are mild and mild, byproducts generated by violent oxidation can be avoided, the safety is higher, and the reaction yield is higher.
Detailed Description
It should be noted that the embodiments and features of the embodiments may be combined with each other without conflict.
This example relates to a process for the preparation of 5(6) -decenoic acid.
The preparation method of this example is designed to synthesize 5(6) -decenoic acid in one step from 2-butylcyclohexanone through carbamide oxidation and isomerization, and based on this overall design idea, the preparation method of this example specifically includes the following steps:
under an ice water bath, adding formic acid into carbamide to obtain a mixture, uniformly stirring, dropwise adding 2-butylcyclohexanone into the mixture, and continuously stirring for reaction to obtain a reaction solution; then, adding water into the reaction liquid for quenching reaction and liquid separation, and mixing, extracting and separating the lower-layer water phase after liquid separation and cyclohexane to obtain an oil phase; then, the separated oil phase is washed to be neutral by water, and then is subjected to desolventizing and rectification, and the fraction at the temperature of 190-230 ℃ is collected to obtain the 5(6) -decenoic acid product.
Wherein, in the preparation step, the percarbamide is added with the formic acid with the concentration of 80-90% by weight, and the weight ratio of the percarbamide to the formic acid is 1: 1-3, the weight ratio of the mixture to the dropwise added 2-butylcyclohexanone is 1:0.1-0.2, and the dropwise adding speed of the 2-butylcyclohexanone is controlled when dropwise adding, so as to keep the temperature of the reaction liquid at 25-40 ℃. And (3) dropwise adding 2-butylcyclohexanone, and continuously stirring for 0.5-3h to obtain a reaction solution, wherein the weight ratio of the reaction solution to water is 1: 1.5. Volume ratio of lower layer aqueous phase to cyclohexane 1: 0.2-1.0, and extracting the lower aqueous phase with cyclohexane under the same conditions for 1-3 times, such as 2 times, each time combining the obtained oil phases together and washing with water. The volume ratio of oil phase to water is 1:2-4 and the oil phase is washed 1-3 times, for example 2 times, with water in a volume ratio of 1: 2-4.
In addition, the desolventizing in the above step is to remove the solvent contained in the washed oil phase under heating, and the solvent is generally one or a mixed solvent of cyclohexane, toluene, benzene and methylcyclohexane. And the oil phase after desolventizing is rectified under the conditions of reduced pressure and heating to remove impurities contained in the oil phase.
More specifically, in the preparation of 5(6) -decenoic acid in this example, if the weight ratio of percarbamide to formic acid is greater than 1:1, the reaction concentration is too high, the heat release is violent, the reaction is not easy to control, and the danger of material flushing is easy to appear. If the weight ratio of percarbamide to formic acid is less than 1: 3, the reaction solution has a low oxygen concentration and a low reaction rate, and therefore, the reaction time needs to be prolonged, which increases the production cost. Thus, the weight ratio of percarbamide to formic acid was set to 1: 1-3 are appropriate, and preferably, the weight ratio of percarbamide to formic acid is 1: 1-2.
In the present embodiment, the formic acid concentration exceeding the range of 80 to 90% by weight is disadvantageous in that too low a concentration causes too much moisture to affect the activity of the percarbamide and makes it difficult to promote the oxidation reaction smoothly, while too high a concentration causes too violent reaction and more side reactions, so that the formic acid concentration may be set to 80 to 90% by weight, and preferably, it may be 85 to 90% by weight.
In this example, if the weight ratio of the mixture to 2-butylcyclohexanone is greater than 1:0.1, the oxidant concentration is higher, the conversion is not significantly increased, but rather the production cost is increased, if the weight ratio of the mixture to 2-butylcyclohexanone is less than 1: 0.2, the amount of the oxidizing agent is insufficient, resulting in incomplete reaction and a decrease in yield. It is therefore appropriate to set the weight ratio of mixture to 2-butylcyclohexanone in the range of 1:0.1 to 0.2, and preferably the weight ratio of mixture to 2-butylcyclohexanone may be selected from 1: 0.12-0.18.
In this embodiment, if the reaction temperature of the reaction solution is higher than 40 ℃, the decomposition rate of the oxidant is high, which may result in the risk of flushing, and if the reaction temperature of the reaction solution is lower than 25 ℃, the decomposition rate of the oxidant is too low, which may result in almost no reaction, so the reaction temperature of the reaction solution is generally set to 25-40 ℃.
For reasons of yield and energy consumption, it is also disadvantageous that the reaction time exceeds the range of 0.5 to 3 hours after the end of the dropwise addition of 2-butylcyclohexanone in the present example, and the reaction time may preferably be 1 to 2.5 hours, and more preferably may be 1 to 2.0 hours.
In this example, if the volume ratio of the lower aqueous phase to cyclohexane is greater than 1: 0.2, the extraction is incomplete, if the volume ratio of the lower aqueous phase to cyclohexane is less than 1: 1.0, the concentration of formic acid in the oil phase is increased, with unnecessary costs. Thus, the volume ratio of the lower aqueous phase to cyclohexane was 1: 0.2 to 1.0 is reasonable, and preferably the volume ratio of the groundwater phase to cyclohexane may be 1: 0.3-0.8, and more preferably it may be 1: 0.4-0.6.
In this example, if the volume ratio of the combined oil phase and water is greater than 1:2, the formic acid is difficult to wash out, if the volume ratio of the combined oil phase and water is less than 1: 4, a large amount of waste water is generated. Based on the principle that washing is carried out a small number of times, the volume ratio of oil phase to water is 1:2-4 are appropriate, and preferably the volume ratio of oil phase to water may be 1: 2.4-3.6, and more preferably it may be 1: 2.8-3.2. In addition, in the present embodiment, the collection of the fraction at 230 ℃ and 190 ℃ is generally carried out when the temperature in the distillation kettle reaches 260 ℃ and 220 ℃ in the distillation process, so as to obtain the desired 5(6) -decenoic acid product.
The 5(6) -decenoic acid product obtained by the preparation method of this example was found to have a 5(6) -decenoic acid content of 85.0-95.0% by weight using a conventional 5(6) -decenoic acid analysis method. The 5(6) -decenoic acid obtained by the preparation method is suitable for preparing essence such as cream, dairy, yoghourt and strawberries.
The preparation process of the present invention will be further illustrated by several preparation examples.
Preparation of example 1
The preparation procedure in this example is as follows:
800g of formic acid having a concentration of 80% by weight was added to 800g of percarbamide in an ice water bath to obtain a mixture, the mixture was stirred uniformly, and 160g of 2-butylcyclohexanone was added dropwise to the mixture while controlling the dropping speed and maintaining the temperature of the reaction solution at 30 ℃. After the dropwise addition, the reaction solution was stirred for 0.5h, and then 2.6kg of water was added to the reaction solution to quench the reaction, followed by liquid separation. The lower aqueous phase was extracted with 1.5L cyclohexane, and the separated oil phases were combined and washed with 4L water to neutrality. Then desolventizing and rectifying, and collecting the fraction at 230 ℃ and 190 ℃ when the temperature in the kettle reaches 260 ℃ and 220 ℃ to obtain 110g of 5(6) -decenoic acid product. The 5(6) -decenoic acid content of this product was determined to be 93.0% by weight.
Preparation of example 2
The preparation procedure in this example is as follows:
1050g of formic acid having a concentration of 88% by weight was added to 350g of percarbamide in an ice water bath to obtain a mixture, and the mixture was stirred uniformly, and 140g of 2-butylcyclohexanone was added dropwise to the mixture while controlling the dropping speed and keeping the temperature of the reaction solution at 25 to 40 ℃. After the dropwise addition, the reaction solution was stirred for 3 hours, and then 2.3kg of water was added to the reaction solution to quench the reaction, followed by liquid separation. The lower aqueous phase was extracted with 2.5L cyclohexane, and the separated oil phases were combined and washed with 12L water to neutrality. Then desolventizing and rectifying, and collecting the fraction at 230 ℃ and 190 ℃ when the temperature in the kettle reaches 260 ℃ and 220 ℃ to obtain 104g of 5(6) -decenoic acid product. The 5(6) -decenoic acid content of this product was determined to be 95.0% by weight.
Preparation of example 3
The preparation procedure in this example is as follows:
284g of formic acid having a concentration of 90% by weight was added to 143g of percarbamide in an ice water bath to obtain a mixture, and the mixture was stirred uniformly, and 62g of 2-butylcyclohexanone was added dropwise to the mixture while controlling the dropping speed and maintaining the temperature of the reaction solution at 25 to 40 ℃. After the dropwise addition, the reaction was continued for 2 hours with stirring, and then 735ml of water was added to the reaction solution to quench the reaction, and the solution was separated. The lower aqueous phase was extracted with 200ml of cyclohexane, and the separated oil phases were combined together and washed with 800ml of water to neutrality. Then desolventizing and rectifying, and collecting the fraction at 230 ℃ and 190 ℃ when the temperature in the kettle reaches 260 ℃ and 220 ℃ to obtain 48g of 5(6) -decenoic acid product. The 5(6) -decenoic acid content of this product was determined to be 88% by weight.
Preparation of example 4
The preparation procedure in this example is as follows:
400g of formic acid having a concentration of 88% by weight was added to 200g of carbamide in an ice water bath to obtain a mixture, and the mixture was stirred uniformly, and 120g of 2-butylcyclohexanone was added dropwise to the mixture while controlling the dropping speed and keeping the temperature of the reaction solution at 25 to 40 ℃. After the dropwise addition, the reaction was continued for 1 hour with stirring, and then 720g of water was added to the reaction solution to quench the reaction, followed by liquid separation. The lower aqueous phase was extracted with 170ml of cyclohexane, and the separated oil phases were combined together and washed with 1L of water to neutrality. Then desolventizing and rectifying, and collecting the fraction at 230 ℃ and 190 ℃ when the temperature in the kettle reaches 260 ℃ and 220 ℃ to obtain 79g of 5(6) -decenoic acid product. The 5(6) -decenoic acid content of this product was determined to be 85% by weight.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. A preparation method of 5(6) -decenoic acid is characterized by comprising the following steps: the preparation method comprises the step of synthesizing 5(6) -decenoic acid by oxidizing and isomerizing 2-butylcyclohexanone through carbamide.
2. The process for the preparation of 5(6) -decenoic acid according to claim 1, characterized in that: under an ice-water bath, adding formic acid into carbamide to obtain a mixture, uniformly stirring, dropwise adding 2-butylcyclohexanone into the mixture, and continuously stirring for reaction to obtain a reaction solution; then, adding water into the reaction liquid for quenching reaction and liquid separation, and mixing, extracting and separating the lower-layer water phase after liquid separation and cyclohexane to obtain an oil phase; then, the separated oil phase is washed to be neutral by water, and then is subjected to desolventizing and rectification, and the fraction with the temperature of 190-230 ℃ is collected to obtain the 5(6) -decenoic acid product.
3. The process for the preparation of 5(6) -decenoic acid according to claim 2, characterized in that: adding 80-90% by weight of formic acid into percarbamide, wherein the weight ratio of the percarbamide to the formic acid is 1: 1-3.
4. The process for the preparation of 5(6) -decenoic acid according to claim 2, characterized in that: the weight ratio of the mixture to the dropwise added 2-butylcyclohexanone is 1:0.1-0.2, and the dropwise adding speed of the 2-butylcyclohexanone is controlled to keep the temperature of the reaction solution at 25-40 ℃.
5. The process for the preparation of 5(6) -decenoic acid according to claim 2, characterized in that: and (3) dropwise adding the 2-butylcyclohexanone, and continuously stirring for 0.5-3h to obtain a reaction solution.
6. The process for the preparation of 5(6) -decenoic acid according to claim 2, characterized in that: the weight ratio of the reaction liquid to water was 1: 1.5.
7. The process for the preparation of 5(6) -decenoic acid according to claim 2, characterized in that: volume ratio of lower layer aqueous phase to cyclohexane 1: 0.2-1.0, and extracting the lower aqueous phase and cyclohexane under the same conditions for 1-3 times, wherein the oil phase obtained in each time is combined together.
8. The process for the preparation of 5(6) -decenoic acid according to claim 2, characterized in that: the volume ratio of oil phase to water is 1:2-4, and washing the oil phase and the water for 1-3 times according to the volume ratio of 1: 2-4.
9. The process for the preparation of 5(6) -decenoic acid according to claim 2, characterized in that: the desolventizing is to remove the solvent contained in the washed oil phase under the heating condition, and the desolventized oil phase is rectified under the conditions of decompression and heating to remove impurities contained in the oil phase.
10. The process for the preparation of 5(6) -decenoic acid according to any one of claims 2 to 9, characterized in that: the 5(6) -decenoic acid product is obtained by collecting the fraction at the temperature of 190-230 ℃ when the temperature in the distillation kettle reaches 220-260 ℃ during rectification, and the content of the 5(6) -decenoic acid in the obtained 5(6) -decenoic acid product is 85-95% by weight.
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|---|---|---|---|---|
| GB1289243A (en) * | 1971-03-25 | 1972-09-13 | ||
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| CN1597655A (en) * | 2004-07-19 | 2005-03-23 | 大连金菊化工厂 | Synthesis of 5(6) caproleic acid |
| CN103864601A (en) * | 2014-03-20 | 2014-06-18 | 广东广益科技实业有限公司 | Process for synthesizing milk lactone |
| CN110128259A (en) * | 2019-06-12 | 2019-08-16 | 广东广益科技实业有限公司 | 5 (6)-decene acid production process |
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- 2019-10-24 CN CN201911015120.8A patent/CN110922324A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1289243A (en) * | 1971-03-25 | 1972-09-13 | ||
| CN1266841A (en) * | 1999-03-11 | 2000-09-20 | 厦门涌泉集团限公司 | Synthesis of 5(6)-caproleic acid |
| CN1597655A (en) * | 2004-07-19 | 2005-03-23 | 大连金菊化工厂 | Synthesis of 5(6) caproleic acid |
| CN103864601A (en) * | 2014-03-20 | 2014-06-18 | 广东广益科技实业有限公司 | Process for synthesizing milk lactone |
| CN110128259A (en) * | 2019-06-12 | 2019-08-16 | 广东广益科技实业有限公司 | 5 (6)-decene acid production process |
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