CN109369360B - Preparation method of 3,6, 6-trimethyl-2, 4-cycloheptadienone - Google Patents
Preparation method of 3,6, 6-trimethyl-2, 4-cycloheptadienone Download PDFInfo
- Publication number
- CN109369360B CN109369360B CN201811244030.1A CN201811244030A CN109369360B CN 109369360 B CN109369360 B CN 109369360B CN 201811244030 A CN201811244030 A CN 201811244030A CN 109369360 B CN109369360 B CN 109369360B
- Authority
- CN
- China
- Prior art keywords
- cycloheptadienone
- trimethyl
- product
- carene
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- 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
- C07C45/28—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation of CHx-moieties
-
- C—CHEMISTRY; METALLURGY
- 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
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/18—Systems containing only non-condensed rings with a ring being at least seven-membered
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2602/00—Systems containing two condensed rings
- C07C2602/02—Systems containing two condensed rings the rings having only two atoms in common
- C07C2602/14—All rings being cycloaliphatic
- C07C2602/20—All rings being cycloaliphatic the ring system containing seven carbon atoms
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a preparation method of 3,6, 6-trimethyl-2, 4-cycloheptadienone. 3-carene on CrO3‑Al2O3Under catalysis with O2Reacting at 35 ℃ for 24h to generate a product I taking 5-carene as a main component, wherein the conversion rate of the 3-carene is about 81.3 percent, and the selectivity of the 5-carene is 60.1 percent; the product I reacts for 4 hours at the temperature of 120 ℃ under the pressure of 0-1 kPa, and is converted into a product II taking 3,6, 6-trimethyl-2, 4-cycloheptadienone as a main component, the conversion rate of 5-carene is 100%, and the selectivity of 3,6, 6-trimethyl-2, 4-cycloheptadienone is 98.7%; and (3) carrying out vacuum rectification on the product II to obtain the 3,6, 6-trimethyl-2, 4-cycloheptadienone, wherein the yield is more than 75%, and the purity is more than 95%.
Description
Technical Field
The invention relates to a preparation method of 3,6, 6-trimethyl-2, 4-cycloheptadienone, in particular to a method for preparing 3,6, 6-trimethyl-2, 4-cycloheptadienone from 3-carene through oxidation and ring opening isomerization.
Background
3,6, 6-trimethyl-2, 4-cycloheptadienone is a heptatomic ketone compound, has a rich and pleasant odor, and is an important perfume. 3,6, 6-trimethyl-2, 4-cycloheptadienone is very similar in molecular structure to that of Uigraflavone (compound 4), but its content in nature is much lower than that of the latter, and it is reported in the literature that a trace amount of 3,6, 6-trimethyl-2, 4-cycloheptadienone is currently found only in black pepper oil and Pinus sylvestris turpentine (Bull Soc. Chim. Belg.,1975,84: 167-.
At present, the research on the properties and the application of 3,6, 6-trimethyl-2, 4-cycloheptadienone is relatively few, and a relatively new result is lacked, and the analysis reason is probably caused by the fact that the natural source is few and the efficient preparation is difficult. The 3,6, 6-trimethyl-2, 4-cycloheptadienone is mainly obtained by catalytic oxidation of 3-carene, common catalysts comprise lead tetraacetate, anhydrous chromium trioxide, potassium permanganate and the like, and the selectivity of the 3,6, 6-trimethyl-2, 4-cycloheptadienone in the product is usually not more than 20% no matter how the reaction process is changed (Khim. Prir. Soediin., 1995,4: 511-; introducing oxygen, and carrying out reflux reaction on the 3-carene, cobalt stearate and NaOH aqueous solution for 4h to generate 48.0 percent of 3,6, 6-trimethyl-2, 4-cycloheptadienone and 11.5 percent of Uygarvone (J.C.S. Perkin I,1975,22: 2232-; also under the catalysis of cobalt stearate and NaOH aqueous solution, 3-carene reacts with oxygen at 50 ℃ for 10h, and the product contains 28.3% of 3,6, 6-trimethyl-2, 4-cycloheptadienone and 19.7% of Uigraketone (Khim. Prir. Soedin.,1991,3: 328-. From the existing research results, the preparation process of 3,6, 6-trimethyl-2, 4-cycloheptadienone has the main problems of low selectivity and difficulty in realizing efficient separation with the simultaneously generated Uigold carvone.
Disclosure of Invention
According to the invention, 3-carene is used as a raw material to prepare 3,6, 6-trimethyl-2, 4-cycloheptadienone, the yield of the product is high, and no Uighurone is generated, so that high-efficiency purification is easily realized by a simpler separation method, and a high-purity product is obtained; moreover, the process of the invention does not need strong base catalysis, and the catalyst can be recycled and easily recovered, and is environment-friendly.
The specific embodiment of the invention is as follows: a preparation method of 3,6, 6-trimethyl-2, 4-cycloheptadienone, wherein allylic oxidation of 3-carene is carried out under the combined action of an oxidant and a catalyst to generate a product I with 5-carene as a main component; the product I reacts at constant temperature under the condition of reduced pressure to be converted into a product II taking 3,6, 6-trimethyl-2, 4-cycloheptadienone as a main component, and the product II is rectified under reduced pressure to obtain the 3,6, 6-trimethyl-2, 4-cycloheptadienone with the purity of more than 95 percent by weight.
The catalyst is CrO3-Al2O3The dosage is 3-5% of the mass of the raw materials.
The oxidant is O2The dosage is 35 mL/min.
The reaction temperature of the allylic oxidation reaction is 30-35 ℃, and the reaction time is 16-24 h.
And recycling the catalyst for 1-2 times.
The reaction process for preparing the product II from the product I comprises the following steps: the reaction pressure is less than or equal to 1kPa, the reaction temperature is 100-140 ℃, and the reaction time is 3-5 h.
Advantageous effects
1. The invention develops a brand new, high-efficiency and environment-friendly preparation process method of 3,6, 6-trimethyl-2, 4-cycloheptadienone; the process product has higher yield, and because no excellent carvone is generated, the process product is easy to realize high-efficiency purification by a simpler separation method, thereby obtaining a high-purity product; moreover, the process of the invention does not need strong base catalysis, and the catalyst can be recycled and easily recovered, and is environment-friendly.
2. The 3,6, 6-trimethyl-2, 4-cycloheptadienone is prepared by using 3-carene as a raw material through low-temperature oxidation and heating under controlled pressure, the raw material is derived from natural resources, and the product can be used as the same as a natural product. Oxygen oxidation was used for maximum production of 5-carone.
Drawings
Compound 2 (5-carone) of FIG. 11H NMR spectrum and13c NMR spectrum; the purity is 97.37%.1H NMR(CDCl3,500MHz)δ:1.04(6H,9-H,10-H),1.19(1H,6-H),1.88(3H,7-H),2.04(1H,2-H-a),2.37(1H,2-H-b),5.82(1H,4-H)；13C NMR(CDCl3,500MHz)δ:23.54(8-C),22.38(9-C,10-C),25.73(7-C),27.72(1-C),28.30(2-C),32.71(6-C),126.21(4-C),158.96(3-C),196.42(5-C)。
FIG. 2 Compound 3(3,6, 6-trimethyl-2, 4-cycloheptadienone)1H NMR spectrum and13c NMR spectrum. The purity is 95.32%.1H NMR(CDCl3,500MHz)δ:1.10(6H,9-H,10-H)，2.01(1H,3-H)，2.60(2H,7-H)，5.77(1H,5-H)，6.03(1H,2-H)，6.09(1H,4-H)；13C NMR(CDCl3,500MHz)δ:26.82(9-C,10-C)(8-C)，27.18(8-C)，32.57(6-C)，53.82(7-C)，126.40(4-C),129.48(3-C),147.48(3-C),149.75(5-C)，199.32(1-C)。
Detailed Description
The invention relates to a preparation method of 3,6, 6-trimethyl-2, 4-cycloheptadienone, wherein 3-carene (compound 1) is subjected to allylic oxidation under the combined action of an oxidant and a catalyst to generate a product I taking 5-carene (compound 2) as a main component; the product I reacts for a certain time at constant temperature under the condition of reduced pressure to be converted into a product II taking 3,6, 6-trimethyl-2, 4-cycloheptadienone (compound 3) as a main component, and the product II is rectified under reduced pressure to obtain the high-purity 3,6, 6-trimethyl-2, 4-cycloheptadienone. The reaction formula of the process of the invention is shown in the following figure.
The process of the invention comprises the following more specific operation steps:
the first step is as follows: preparing an oxidation catalyst: weighing a certain amount of anhydrous CrO3Prepared as 5% CrO3Aqueous solution, to be mixed with CrO3Adding neutral alumina with equal mass into the solution, stirring at room temperature for 12-24 h, filtering, and drying a filter cake to obtain an oxidation catalyst;
the second step is that: oxidation to produce product i: adding 3-carene and a transition metal oxidant accounting for 3% -5% of the mass of the 3-carene into a reaction bottle, introducing oxygen from the bottom of the reaction bottle, controlling the ventilation amount to be 35mL/min, stirring and reacting at 30-35 ℃ for 16-24 h, sampling at regular time, tracking the reaction, and stopping the reaction when the content of 5-carone is not obviously increased any more;
the third step: catalyst recovery: centrifuging or filtering the reaction liquid obtained in the second step, and using the recovered catalyst for the next reaction;
the fourth step: preparation of product II: transferring the filtrate obtained in the third step into a reaction bottle, connecting the reaction bottle with a vacuum system, vacuumizing to 0-1 kPa, heating to 100-140 ℃, reacting for 3-5 h, stopping heating, removing vacuum, sampling, analyzing, and stopping reaction if no 5-carone exists in the reaction liquid;
the fifth step: preparation of 3,6, 6-trimethyl-2, 4-cycloheptadienone: and carrying out reduced pressure rectification on the reaction product obtained in the fourth step, wherein the vacuum degree is 0-1 kPa, the kettle temperature is 120-140 ℃, and collecting to obtain the 3,6, 6-trimethyl-2, 4-cycloheptadienone.
Example 1
5g of anhydrous CrO are weighed3Preparing a 5% aqueous solution, weighing 5g of neutral alumina (100 meshes), adding the neutral alumina into the aqueous solution, stirring at room temperature for 24 hours, filtering, and drying at 110 ℃ for 6 hours; weighing 100g of 3-carene and 5.0g of CrO3-Al2O3Adding the materials into a reaction bottle together, introducing oxygen, controlling the air inflow to be 35mL/min, and starting stirring to react; timing when the temperature reaches 35 ℃, sampling every 1h, centrifugally separating the catalyst, and performing gas chromatography analysis; gas phase analysis results after 24 h: 3-carene 18.64%, 5-carone 48.92%, analysis after 25h gave: and 3-carene 18.19% and 5-carene 48.57% stop the reaction, and centrifugally treating the reaction liquid to recover the catalyst.
Example 2
The catalyst is recycled for the 2 nd time, other process conditions are the same as those of the example 1, and the gas phase analysis result after 24 hours is as follows: 3-carene 23.62%, 5-carone 42.59%.
Example 3
The reaction temperature is 30 ℃, the other process conditions are the same as those of the example 1, and the gas phase analysis result after 24 hours is as follows: 3-carene 21.61%, 5-carone 43.04%.
Example 4
Example 1 after recovering the catalyst, the liquid was transferred to a reaction flask, evacuated to 0.25kPa, heated to 120 ℃, reacted for 4 hours while timing, the heating was stopped, the vacuum was released, and a sample was taken for gas chromatography, and as a result: 3-carene 16.12%, 3,6, 6-trimethyl-2, 4-cycloheptadienone 47.96%, and no 5-carene exists.
Example 5
Vacuum is pumped to 0.67kPa, the other process conditions are the same as in example 4, and the gas phase analysis results are as follows: 3-carene 16.97%, 3,6, 6-trimethyl-2, 4-cycloheptadienone 47.62%, 5-carene 0.43%.
Example 6
The reaction temperature was 100 ℃, the other process conditions were the same as in example 4, and the gas phase analysis results were: 17.13 percent of 3-carene, 43.76 percent of 3,6, 6-trimethyl-2, 4-cycloheptadienone and 4.68 percent of 5-carene.
Example 7
The reaction time is 2h, the other process conditions are the same as example 4, and the gas phase analysis result is as follows: 17.64 percent of 3-carene, 38.37 percent of 3,6, 6-trimethyl-2, 4-cycloheptadienone and 9.84 percent of 5-carene.
Example 8 comparative example
The reaction is carried out under normal pressure, the other process conditions are the same as those in example 4, and the gas phase analysis result is as follows: 17.48% of 3-carene, 48.13% of 5-carene and no 3,6, 6-trimethyl-2, 4-cycloheptadienone.
It can be seen from this that the product II whose main component is 3,6, 6-trimethyl-2, 4-cycloheptadienone was obtained by controlling the reaction conditions and heating the reaction under reduced pressure.
Example 9
460.7g of reaction product II (the content of 3,6, 6-trimethyl-2, 4-cycloheptadienone is 45.26 percent) is rectified under reduced pressure, the vacuum degree is 0.3kPa, 164.7g of 3,6, 6-trimethyl-2, 4-cycloheptadienone is collected at the kettle temperature of 120-140 ℃, and the purity is 95.32 percent.
Claims (3)
1. A preparation method of 3,6, 6-trimethyl-2, 4-cycloheptadienone is characterized by comprising the following steps: allylic oxidation of 3-carene is carried out under the combined action of an oxidant and a catalyst to generate a product I taking 5-carene as a main component; the product I is reacted at constant temperature under the condition of reduced pressure and is converted into a product II taking 3,6, 6-trimethyl-2, 4-cycloheptadienone as a main component, and the product II is rectified under reduced pressure to obtain 3,6, 6-trimethyl-2, 4-cycloheptadienone with the purity of more than 95 percent by weight; the catalyst is CrO3-Al2O3The using amount is 3% -5% of the mass of the raw materials; the oxidant is O2The dosage is 35 mL/min; the reaction process for preparing the product II from the product I comprises the following steps: the reaction pressure is less than or equal to 1kPa, and the reaction temperature isThe reaction time is 3-5 h at 100-140 ℃.
2. The process for producing 3,6, 6-trimethyl-2, 4-cycloheptadienone as claimed in claim 1, wherein: the reaction temperature of the allylic oxidation reaction is 30-35 ℃, and the reaction time is 16-24 h.
3. The process for producing 3,6, 6-trimethyl-2, 4-cycloheptadienone as claimed in claim 1, wherein: and recycling the catalyst for 1-2 times.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811244030.1A CN109369360B (en) | 2018-10-24 | 2018-10-24 | Preparation method of 3,6, 6-trimethyl-2, 4-cycloheptadienone |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811244030.1A CN109369360B (en) | 2018-10-24 | 2018-10-24 | Preparation method of 3,6, 6-trimethyl-2, 4-cycloheptadienone |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109369360A CN109369360A (en) | 2019-02-22 |
| CN109369360B true CN109369360B (en) | 2021-09-03 |
Family
ID=65401171
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811244030.1A Active CN109369360B (en) | 2018-10-24 | 2018-10-24 | Preparation method of 3,6, 6-trimethyl-2, 4-cycloheptadienone |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109369360B (en) |
-
2018
- 2018-10-24 CN CN201811244030.1A patent/CN109369360B/en active Active
Non-Patent Citations (1)
| Title |
|---|
| Homogeneous Catalysed Autoxidation of Car-3-ene, α-Pinene and Tetralin;D MUKESH et al;《The Chemical Engineering Journal》;1989;第41卷;67-74 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109369360A (en) | 2019-02-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106977380B (en) | At low pressure CO2Method for preparing cyclohexanone by phenol hydrogenation in environment | |
| CN108707076A (en) | A kind of preparation method of 4- acetoxyl-2-methyl-2-butylenoic aldehydes | |
| CN110548538A (en) | Preparation method and application of metal modified SAPO-34 molecular sieve | |
| CN109369360B (en) | Preparation method of 3,6, 6-trimethyl-2, 4-cycloheptadienone | |
| CN112321557B (en) | Preparation method of Jiale musk | |
| CN110372653B (en) | Selenylation benzofuran compound and synthesis method thereof | |
| CN107540531B (en) | Method for preparing o-chlorocyclohexanone by using cyclohexanone byproduct light oil | |
| CN110981724B (en) | Method for preparing 4-acetoxyl-2-methyl-2-butenal | |
| CN106278854B (en) | A kind of preparation method by α-isophorone isomery β-isophorone | |
| CN112645813B (en) | Preparation method of (R) -3-cyclohexene carboxylic acid | |
| CN113072461B (en) | Preparation method of butanone oxime | |
| CN102731281A (en) | Method for preparing coarse fluorene and fluorenone by taking wash oil as raw material | |
| CN104016995A (en) | Octa-substituted perfluoroalkyl cobalt phthalocyanine compound and preparation method thereof | |
| CN110835296B (en) | Preparation process of 2,2, 4-trimethyl-3-hydroxypentanoic acid | |
| WO2007073240A1 (en) | Catalyst, a method for the production thereof and a dihydroxyalkane production method | |
| CN103224445B (en) | Technology for preparing resorcinol by direct oxidation of benzene | |
| CN112574017A (en) | Preparation method of low-color-number citronellol | |
| CN112225645B (en) | Preparation method of m-cresol | |
| CN111440055B (en) | Synthesis method of beta-damascone | |
| CN104447531A (en) | Preparation method of 3,5-dibromopyridine-N-oxide | |
| CN113731492B (en) | Recyclable cobalt-manganese composite catalyst, preparation method and application thereof in acetophenone preparation | |
| CN113731400B (en) | K 7 [MnV 13 O 38 ]·18H 2 Application of O as catalyst in aromatic hydrocarbon hydroxylation reaction | |
| CN113582860B (en) | Preparation method of N-methyl monoethanolamine | |
| CN106854196B (en) | A kind of synthesis technology of organic synthesis intermediate cyclohexanone ethylene ketal | |
| CN107827723A (en) | A kind of long-chained acyclic diketone synthetic method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |