CN113234051B - Preparation method of Jiale musk - Google Patents
Preparation method of Jiale musk Download PDFInfo
- Publication number
- CN113234051B CN113234051B CN202110605862.7A CN202110605862A CN113234051B CN 113234051 B CN113234051 B CN 113234051B CN 202110605862 A CN202110605862 A CN 202110605862A CN 113234051 B CN113234051 B CN 113234051B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- cerium
- mass fraction
- preparation
- containing compound
- 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
- C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D311/94—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems condensed with rings other than six-membered or with ring systems containing such rings
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a preparation method of galaxolide, under the action of a supported cerium catalyst, 1,1,2,3,3, 5-hexamethylindane and propylene oxide undergo alkylation reaction, then dehydration condensation cyclization is carried out to generate galaxolide, and the product is separated out through continuous rectification. The invention avoids the problems of complex process, low utilization rate of raw materials, low safety and the like in the prior art, and has simple process, the conversion rate of the raw materials is more than 95 percent, and the selectivity of the product is more than 92 percent.
Description
Technical Field
The invention relates to a production method of galaxolide, in particular to a method for producing galaxolide by alkylation reaction of 1,1,2,3,3, 5-hexamethylindane and propylene oxide and dehydration, condensation and cyclization, belonging to the technical field of chemical industry.
Technical Field
Galaxolide (Galaxolide) belongs to a synthetic tricyclic isochroman musk, is used as a substitute of natural musk, and is widely applied to essence and spice and daily chemical industry. The galaxolide musk has good light stability and high fragrance quality, and is the product with the most development potential in polycyclic musk.
The existing process in China mostly adopts 1,1,2,3, 3-pentamethyl indane to obtain an intermediate hexamethyl indanol through alkylation reaction, and then the hexamethyl indanol and paraformaldehyde form ether cyclization to obtain galaxolide, the process is complicated, excessive pentamethyl indane or chlorobenzene with high toxicity is used as a reaction solvent in the process, the cost is high, the energy consumption is high, and the yield is low; the etherification reaction of paraformaldehyde needs to be catalyzed by HCl gas, and a highly toxic byproduct, namely chloromethyl ether, can be generated, so that the method has great potential safety hazard and serious corrosion to equipment.
Aiming at the defects in the process, a novel preparation method of galaxolide musk is urgently needed to be developed, and the problems of complex and tedious process, low reaction yield, high production cost, serious equipment corrosion, low safety, environmental friendliness and the like in the existing production are solved.
Disclosure of Invention
One of the objects of the present invention is to provide a novel process for the preparation of galaxolide.
In order to realize the purpose, the invention provides a preparation method of galaxolide, and particularly relates to a method for preparing galaxolide by alkylation reaction of 1,1,2,3,3, 5-hexamethylindane and propylene oxide, dehydration condensation and cyclization under the action of a supported Ce catalyst, wherein galaxolide can be obtained by one pot of hexamethylindane, the process flow is simple, and the reaction yield is high; meanwhile, the use of solvents such as pentamethyl indane, paraformaldehyde and HCl gas is avoided, and the cost and potential safety hazards are reduced. And the method uses the supported Ce catalyst, the catalyst is environment-friendly, easy to separate, free from loss and simple in post-treatment, and is suitable for industrial production.
The adopted scheme comprises the following steps:
a preparation method of Jiale musk comprises the following steps: under the action of a supported cerium catalyst, preferably in a dichloromethane solvent, 1,1,2,3,3, 5-hexamethylindane and propylene oxide are subjected to alkylation reaction, then dehydration condensation cyclization is carried out to generate galaxolide, and the product is separated out through continuous rectification.
The reaction route of the invention is as follows:
in the preparation method, the dosage of the supported Ce catalyst is 4-10 wt% relative to the mass of 1,1,2,3,3, 5-hexamethylindane.
In the preparation method, the molar ratio of the 1,1,2,3,3, 5-hexamethylindane to the propylene oxide is 1:1-1:1.2, preferably 1:1.05-1: 1.13.
In the preparation method, the feeding mass ratio of the dichloromethane solvent to the propylene oxide is 3:1-5:1, preferably 3.7:1-4.5: 1. In the preparation method, the reaction temperature is-10-30 ℃; the reaction time is 3-9 h.
In the preparation method, the product can be rectified by a known method, such as triangular spiral packing, the number of plates is 25-40, the reflux ratio is 2-4, the pressure is 2-10hPa, and the temperature of the tower bottom is 160-.
A second aspect of the invention relates to a supported Ce catalyst for use in the preparation of galaxolide.
A supported cerium catalyst, denoted Ce-Z-X/Y. In the catalyst, Ce is an active component; z is a cocatalyst selected from one or more of Ag, Cu, Al, Zn, Ni, Re, Sn, Sc, Cr and Mn, preferably one or more of Al, Ni, Sc and Mn; x is a ligand, and is selected from one or more of 1-aminobenzotriazole, 5-methylbenzotriazole, 2' -bipyridine, 4' - (4-benzonitrile) -2,2':6', 2' -terpyridine, 1-benzoylpiperazine and phenanthroline, preferably 5-methylbenzotriazole and/or 1-benzoylpiperazine; y is a carrier and is selected from one or more of neutral alumina, silica, kaolin, diatomite, ordered mesoporous carbon and molecular sieves, and preferably from one or more of neutral alumina, silica and 4A molecular sieves.
In the catalyst, based on the total weight of the catalyst (calculated by Ce element + Z element + X + Y), the mass fraction of Ce is 2-15%, Z is 15-25%, X is 20-45%, and Y is 30-50%; preferably, the mass fraction of Ce is 5-10%, the mass fraction of Z is 18-23%, the mass fraction of X is 25-40%, and the mass fraction of Y is 35-45%.
The invention also provides a preparation method of the catalyst, which is realized by the following scheme:
in the invention, the preparation method of the supported Ce catalyst comprises the following steps:
(1) mixing a Ce-containing compound and a ligand X in water, then dripping a Z-containing compound aqueous solution, fully stirring, dispersing a carrier Y in the mixed aqueous solution, and fully stirring at 80-95 ℃ to obtain slurry;
(2) and filtering, washing and drying the slurry, and roasting, crushing and tabletting to obtain the supported cerium catalyst.
In the preparation method of the catalyst, in the step (1), the amount of water used is not particularly limited, and the Ce-containing compound, the Z-containing compound, and X added may be completely dissolved.
In the preparation method of the catalyst, in the step (1), the cerium-containing compound is selected from one or more of cerium chloride, cerium nitrate, cerium oxalate and cerium acetate, preferably cerium chloride; the Z-containing compound is selected from soluble salts of Z, such as, but not limited to, acetate, nitrate, hydrochloride, and the like.
In the preparation method of the catalyst, in the step (2), the drying temperature is 90-130 ℃, and the drying time is 8-12 h; the roasting temperature is 400-500 ℃, and the roasting time is 2-4 h.
The invention has the positive effects that:
1. the method has a simple process route, and the galaxolide can be obtained by hexamethylindan in one pot, so that the problems of high cost, large potential safety hazard, environment friendliness and the like caused by the use of solvents, pentamethylindan, paraformaldehyde and HCl gas in the prior art are solved.
2. According to the novel supported Ce catalyst, the coordination bond formed by the lone pair electrons on N in the catalyst framework and Ce is very stable, and the coordination bond is easy to interact with a benzene ring, so that the concentration of a reactant on the surface of the catalyst is increased, and the alkylation reaction and the cyclization reaction are promoted; the active component of the catalyst is matched with the cocatalyst, so that the reaction activity of the condensation cyclization reaction can be improved, and the generation of byproducts can be effectively inhibited; and the catalyst is environment-friendly, the post-treatment is simple, and the problem of environmental pollution can be avoided.
3. The invention can obtain galaxolide musk through alkylation, dehydration, condensation and cyclization under simpler operation conditions, the conversion rate of raw materials reaches more than 95%, and the selectivity of products is more than 92%.
Detailed Description
The present invention is further described in detail with reference to the following examples, but the scope of the present invention is not limited to these examples.
Gas chromatography analysis conditions of the product: shimadzu gas chromatograph, RTX-DB-5 column, injection port temperature: 320 ℃; detector temperature: 350 ℃; temperature rising procedure: keeping at 80 deg.C for 2min, and heating to 200 deg.C at 10 deg.C/min; raising the temperature to 350 ℃ at the temperature of 20 ℃/min, and keeping the temperature for 5 min.
The sources of the apparatus and reagents in the following examples are shown in table 1 below:
TABLE 1
| Instrument and reagent | Source | Specification of |
| ICP spectrometer | Agilent | ICP-OES 720 model |
| Gas chromatograph | Shimadzu | GC-2014C |
| Nuclear magnetic resonance spectrometer | Bruker | Advance Bruker 400M |
| 1,1,2,3,3, 5-hexamethylindane | Aladdin | >97％ |
| Propylene oxide | Aladdin | >99％ |
The inorganic salts used in the following examples are commercially available unless otherwise specified.
Example 1
Mixing 7.6g of cerium chloride and 25.8g of 5-methylbenzotriazole in 500g of distilled water, adding 97.8g of aluminum chloride and 36.1g of 4A molecular sieve under the stirring state, heating to 80 ℃, and stirring for 8 hours to obtain slurry;
and filtering the slurry, washing with deionized water to obtain a filter cake, drying the filter cake at 90 ℃ for 8h, roasting at 500 ℃ for 2h, crushing, tabletting and forming to obtain the catalyst 1. ICP analysis determines that in the catalyst 1, the following components in percentage by mass of the total mass of the catalyst 1 are: 5% of Ce, 23% of Al, 30% of 5-methylbenzotriazole and 42% of 4A molecular sieve.
Example 2
9.9g of cerium chloride and 32.7g of 1-benzoylpiperazine were mixed with 300g of distilled water, and 61.7g of manganese acetate (CH) was added thereto under stirring 3 COO) 2 Mn and 35.5g of neutral alumina, heating to 85 ℃, and stirring for 6 hours to obtain slurry;
and filtering the slurry, washing with deionized water to obtain a filter cake, drying the filter cake at 100 ℃ for 10h, roasting at 450 ℃ for 3h, crushing, tabletting and forming to obtain the catalyst 2. ICP analysis determines that the following components in the catalyst 2 account for the total mass of the catalyst 2 in percentage by mass: ce 6%, Mn 21%, 1-benzoyl piperazine 35%, neutral alumina 38%.
Example 3
Mixing 22.8g of cerium nitrate and 46.55g of 5-methylbenzotriazole in 500g of distilled water, adding 68.3g of nickel nitrate and 44.1g of silicon dioxide under the stirring state, heating to 90 ℃, and stirring for 4 hours to obtain slurry;
and filtering the slurry, washing with deionized water to obtain a filter cake, drying the filter cake at 120 ℃ for 10h, roasting at 400 ℃ for 4h, crushing, tabletting and forming to obtain the catalyst 3. ICP analysis determines that the following components in the catalyst 3 account for the total mass of the catalyst 3 in percentage by mass: ce 8%, Ni 18%, 5-methylbenzotriazole 38% and silicon dioxide 36%.
Example 4
Mixing 17.4g of cerium acetate and 19.3g of phenanthroline in 300g of distilled water, adding 51.8g of scandium chloride and 34.7g of neutral alumina under the stirring state, heating to 95 ℃, and stirring for 3 hours to obtain slurry;
and filtering the slurry, washing with deionized water to obtain a filter cake, drying the filter cake at 130 ℃ for 12h, roasting at 450 ℃ for 3.5h, crushing, tabletting and forming to obtain the catalyst 4. ICP analysis determines that the following components in the catalyst 4 account for the total mass of the catalyst 4 in percentage by mass: 10% of Ce, 20% of Sc, 25% of phenanthroline and 45% of silicon dioxide.
Example 5
Catalyst 1(11.3g, 7 wt%) and 1,1,2,3,3, 5-hexamethylindan (161.9g, 0.8mol) were charged to a reaction kettle equipped with a mechanical stirrer, thermocouple, condenser, and propylene oxide (48.8g, 0.84mol) dissolved in the solvent dichloromethane (195g, 2.30mol) was added dropwise over 2h while maintaining the reaction temperature at about 20 ℃ using an external cooling bath. After the end of the dropwise addition, the reaction mixture was warmed to 30 ℃ and stirred for a further 3 h. Filtering to remove the solid catalyst, separating out reaction liquid, rectifying the obtained crude mixture, wherein the rectification conditions are as follows: triangular spiral packing, 30 tower plates, a reflux ratio of 2.5, a pressure of 2hPa and a tower bottom temperature of 165 ℃ to obtain the galaxolide product with a boiling point of 135-150 ℃.
And (3) nuclear magnetic analysis result of the product:
1 H NMR(CDCl 3 ,400MHz):δ7.31(s,1H),7.13(s,1H),4.68(s,2H),3.70(m,2H),3.31(m,1H),2.14(q,J＝6.8Hz,1H),1.43(s,12H),1.16(d,J＝7.0Hz,3H),1.00(d,J＝6.8Hz,3H).
example 6
Catalyst 2(30.4g, 10 wt%) and 1,1,2,3,3, 5-hexamethylindan (303.5g, 1.5mol) were charged to a reaction kettle equipped with a mechanical stirrer, thermocouple, condenser, and propylene oxide (93.2g, 1.61mol) dissolved in the solvent dichloromethane (344.8g, 4.06mol) was added dropwise over 1h while maintaining the reaction temperature at about-5 ℃ using an external cooling bath. After the end of the dropwise addition, the reaction mixture was warmed to 25 ℃ and stirred for a further 5 h. Filtering to remove the solid catalyst, separating out reaction liquid, rectifying the obtained crude mixture, wherein the rectification conditions are as follows: triangular spiral packing, 30 tower plates, a reflux ratio of 2.5, a pressure of 2hPa and a tower bottom temperature of 165 ℃ to obtain the galaxolide product with a boiling point of 135-150 ℃.
Example 7
Catalyst 3(18.6g, 4 wt%) and 1,1,2,3,3, 5-hexamethylindan (465.4g, 2.3mol) were charged to a reaction kettle equipped with a mechanical stirrer, thermocouple, condenser, and propylene oxide (146.9g, 2.5mol) dissolved in the solvent dichloromethane (587.6g, 6.92mol) was added dropwise over 1h while maintaining the reaction temperature at about 0 ℃ using an external cooling bath. After the end of the dropwise addition, the reaction mixture was warmed to 30 ℃ and stirred for a further 7 h. Filtering to remove the solid catalyst, separating out reaction liquid, rectifying the obtained crude mixture, wherein the rectification conditions are as follows: triangular spiral packing, 30 tower plates, a reflux ratio of 2.5, a pressure of 2hPa and a tower bottom temperature of 165 ℃ to obtain the galaxolide product with a boiling point of 135-150 ℃.
Example 8
Catalyst 4(27.5g, 8 wt%) and 1,1,2,3,3, 5-hexamethylindan (344.0g, 1.7mol) were charged to a reaction kettle equipped with a mechanical stirrer, thermocouple, condenser, and propylene oxide (111.2g, 1.9mol) dissolved in the solvent dichloromethane (478.16g, 5.63mol) was added dropwise over 1h while maintaining the reaction temperature at about 10 ℃ using an external cooling bath. After the end of the dropwise addition, the reaction mixture was warmed to 25 ℃ and stirred for a further 9 h. Filtering to remove the solid catalyst, separating out reaction liquid, rectifying the obtained crude mixture, wherein the rectification conditions are as follows: triangular spiral packing, 30 tower plates, a reflux ratio of 2.5, a pressure of 2hPa and a tower bottom temperature of 165 ℃ to obtain the galaxolide product with a boiling point of 135-150 ℃.
The results for examples 5-8 are shown in Table 2:
TABLE 2
| Catalyst and process for preparing same | Conversion of hexamethylindane% | Selectivity of galaxolide musk |
| 1 | 95.2 | 92.7 |
| 2 | 98.3 | 97.4 |
| 3 | 96.1 | 95.3 |
| 4 | 96.7 | 93.8 |
Claims (13)
1. A preparation method of Jiale musk comprises the following steps: under the action of a supported cerium catalyst, 1,1,2,3,3, 5-hexamethylindane and propylene oxide react in a solvent to generate reaction liquid containing galaxolide, and a product is obtained by continuous rectification and separation; the supported cerium catalyst is represented as Ce-Z-X/Y;
wherein Z is a cocatalyst selected from one or more of Ag, Cu, Al, Zn, Ni, Re, Sc, Cr and Mn;
x is a ligand selected from one or more of 1-aminobenzotriazole, 5-methylbenzotriazole, 2' -bipyridine, 4' - (4-benzonitrile) -2,2':6', 2' -terpyridine, 1-benzoylpiperazine and phenanthroline;
y is carrier selected from one or more of neutral alumina, silicon dioxide, kaolin, diatomite, ordered mesoporous carbon and molecular sieve.
2. The process of claim 1, wherein the solvent is dichloromethane.
3. The process according to claim 1, wherein the catalyst is used in an amount of 4 to 10 wt% with respect to the mass of 1,1,2,3,3, 5-hexamethylindane.
4. The method according to any one of claims 1 to 3, wherein the molar ratio of 1,1,2,3,3, 5-hexamethylindane to propylene oxide is from 1:1 to 1: 1.2.
5. The method according to claim 4, wherein the molar ratio of 1,1,2,3,3, 5-hexamethylindane to propylene oxide is 1:1.05-1: 1.13.
6. The method according to any one of claims 1 to 3, wherein the reaction temperature is-10 to 30 ℃ and the reaction time is 3 to 9 hours.
7. The process according to any one of claims 1 to 3, wherein the supported cerium catalyst is represented by Ce-Z-X/Y;
wherein Z is one or more of Al, Ni, Sc and Mn;
x is 5-methylbenzotriazole and/or 1-benzoyl piperazine;
y is one or more of neutral alumina, silicon dioxide and 4A molecular sieve.
8. The preparation method according to claim 1, wherein the mass fraction of Ce is 2-15%, the mass fraction of Z is 15-25%, the mass fraction of X is 20-45%, and the mass fraction of Y is 30-50%, based on the total weight of the catalyst.
9. The preparation method according to claim 8, wherein the mass fraction of Ce is 5-10%, the mass fraction of Z is 18-23%, the mass fraction of X is 25-40%, and the mass fraction of Y is 35-45%, based on the total weight of the catalyst.
10. The preparation method according to claim 1 or 8, wherein the preparation process of the catalyst comprises the following steps:
(1) mixing a Ce-containing compound and a ligand X in water, then dripping an aqueous solution of a Z-containing compound, fully stirring to obtain a mixed aqueous solution, dispersing a carrier Y in the mixed aqueous solution, and fully stirring at 80-95 ℃ to obtain slurry;
(2) and filtering, washing and drying the slurry, and roasting, crushing and tabletting to obtain the supported cerium catalyst.
11. The method according to claim 10, wherein in the step (1), the cerium-containing compound is one or more selected from cerium chloride, cerium nitrate, cerium oxalate and cerium acetate; and/or the Z-containing compound is selected from soluble salts of Z.
12. The method according to claim 11, wherein the cerium-containing compound is cerium chloride; and/or, the Z-containing compound is selected from acetate, nitrate and hydrochloride of Z.
13. The method according to any one of claims 11 to 12, wherein in the step (2), the drying temperature is 90 to 130 ℃ and the drying time is 8 to 12 hours; and/or the roasting temperature is 400-500 ℃, and the roasting time is 2-4 h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110605862.7A CN113234051B (en) | 2021-06-01 | 2021-06-01 | Preparation method of Jiale musk |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110605862.7A CN113234051B (en) | 2021-06-01 | 2021-06-01 | Preparation method of Jiale musk |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113234051A CN113234051A (en) | 2021-08-10 |
| CN113234051B true CN113234051B (en) | 2022-09-20 |
Family
ID=77136021
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110605862.7A Active CN113234051B (en) | 2021-06-01 | 2021-06-01 | Preparation method of Jiale musk |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113234051B (en) |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4162256A (en) * | 1978-04-19 | 1979-07-24 | International Flavors & Fragrances Inc. | Process for the production of compounds useful in perfumery |
| US9233944B2 (en) * | 2012-06-27 | 2016-01-12 | University Of Kansas | Alkylene epoxidation with mesoporous catalysts |
| CN108250175A (en) * | 2018-02-05 | 2018-07-06 | 杭州更蓝生物科技有限公司 | A kind of synthesis technology of Jiale muskiness |
-
2021
- 2021-06-01 CN CN202110605862.7A patent/CN113234051B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN113234051A (en) | 2021-08-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101812145B (en) | Alpha-nickel diimine compound olefin polymerization catalyst, preparation method and method for preparing branched polyethylene | |
| CN101531725B (en) | Alpha-nickel diimine compound olefin polymerization catalyst and preparation method thereof, and method for preparing branched polyethylene | |
| CN101412771A (en) | Pyridine diimine iron olefin polymerizing catalyst, as well as preparation method and application thereof | |
| CN102875327A (en) | Technique for preparing absolute ethanol from near-azeotropic-concentration ethanol-water mixture | |
| CN112321557B (en) | Preparation method of Jiale musk | |
| CN113620813A (en) | Preparation method of N, N-dimethyl-1, 3-propane diamine | |
| CN102285867B (en) | Synthesis method of 3-hexyne-2,5-diol | |
| CN109796406B (en) | Br nsted-Lewis double-acid ionic liquid and method for catalytically synthesizing succinate by using Br nsted-Lewis double-acid ionic liquid | |
| CN102399119A (en) | Method for catalyzing ethylene oligomerization by using butyryl-substituted 1,10-phenanthroline complex | |
| CN113234051B (en) | Preparation method of Jiale musk | |
| CN111170829B (en) | Preparation method of hexamethyl indanol | |
| CN100491324C (en) | Method and apparatus for continuously preparing ethyl acetate by single tower | |
| US6881864B2 (en) | Production method of xylylenediamine | |
| CN107199051B (en) | A kind of copper heterogeneous catalyst of pyridine coordination and preparation method thereof | |
| CN108947758A (en) | A method of catalysis dibenzofurans open loop prepares biphenyl | |
| CN104529730B (en) | A kind of method being prepared propione by 2-amylene | |
| CN115433067B (en) | Preparation method of beta-isophorone | |
| CN102367230A (en) | Method for synthesizing nitrile from aldoxime | |
| CN112094171B (en) | Method for synthesizing m-chlorotoluene through isomerization reaction | |
| CN112694427B (en) | Method for preparing 2, 3-dimethyl sulfide | |
| CN104447255B (en) | A kind of method being prepared 2 pentanone by 2-amylene | |
| CN102503806A (en) | Method for synthesis of 1,3,5,7-tetra(4-acrylatophenyl)adamantine compound | |
| CN111790437A (en) | Strontium-tantalum-titanium trimetal oxide catalyst for preparing 2-pentanone by liquid phase method ethanol and preparation method and application thereof | |
| CN114516781B (en) | Preparation method of perfluorooctyl ethyl iodide and perfluorooctyl ethylene | |
| CN109574852A (en) | A method of nitrobenzene is prepared using dinitrogen pentoxide nitrification benzene |
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 |