CN109485565B - Preparation method of 1-methyl cyclohexyl methacrylate - Google Patents
Preparation method of 1-methyl cyclohexyl methacrylate Download PDFInfo
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- CN109485565B CN109485565B CN201811380776.5A CN201811380776A CN109485565B CN 109485565 B CN109485565 B CN 109485565B CN 201811380776 A CN201811380776 A CN 201811380776A CN 109485565 B CN109485565 B CN 109485565B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/14—Preparation of carboxylic acid esters from carboxylic acid halides
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/36—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal
- C07C29/38—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal by reaction with aldehydes or ketones
- C07C29/40—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal by reaction with aldehydes or ketones with compounds containing carbon-to-metal bonds
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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
- C07C2601/14—The ring being saturated
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Abstract
The application relates to a preparation method of 1-methylcyclohexyl methacrylate, which comprises the following steps: s1: under the protection of inert gas and in the presence of at least a first catalyst, a second catalyst and a polymerization inhibitor, reacting 1-methylcyclohexanol with methacryloyl chloride in an organic solvent to obtain a reaction mixture containing 1-methylcyclohexyl methacrylate; s2: washing the first reaction mixture with water, an acidic solution, water and an alkaline solution in sequence, and layering to obtain a fourth water phase and a fourth organic phase; s3: and drying, concentrating and rectifying the fourth organic phase under reduced pressure, and collecting main fraction after the temperature is stabilized at about 68 ℃ for 5 minutes to obtain colorless transparent liquid 1-methyl cyclohexyl methacrylate. The method has the beneficial effects that the reaction of the 1-methyl cyclohexanol and the methacryloyl chloride is catalyzed by simultaneously adopting the linear alkyl amine and the aromatic amine as the catalysts, so that the product yield can be obviously improved, and the impurity content in the product is reduced.
Description
Technical Field
The application relates to the technical field of organic chemical synthesis. In particular, the application relates to a preparation method of 1-methylcyclohexyl methacrylate.
Background
Polymethacrylates are the main resin of 193nm photoresist, and the main component of the film-forming resin is alicyclic polymer. The main chain of the acrylate photoresist film-forming resin is generally a polymer of methylene, which mainly has the function of providing film-forming property and mechanical property required by the processing process, and the imaging force, the adhesion, the developability and most of the corrosion resistance of the acrylate photoresist film-forming resin are all born by side chains. Therefore, the side chain design of the host resin is particularly critical.
Because of the linear structure of the main chain (low C/H ratio) and poor dry etching resistance, in order to meet the requirement, large aliphatic groups such as cyclohexane, lauryl, adamantyl and the like are generally introduced into the side chain when film-forming resin of 193nm photoresist is designed, so that the penetrating power and the dispersing power of organic alkali can be controlled, and an effective and balanced controllable part is formed. Meanwhile, methyl is further introduced into the ring of the side chain, so that the corrosion resistance and the adhesion of the photosensitive resin monomer can be improved, and the photosensitive resin monomer with excellent chemical resistance is provided.
The patent JPWO2016125782A1 relates to the synthesis of 1-ethylcyclohexyl methacrylate, and the prior patent directly adopts 1-ethylcyclohexanol to react with methacryloyl chloride to prepare the 1-ethylcyclohexyl methacrylate. The synthetic route is as follows:
in the prior art, 1-ethyl cyclohexyl methacrylate is synthesized by directly reacting 1-ethyl cyclohexanol with methacryloyl chloride. Other 1-alkyl substituted cyclohexyl methacrylates are not directly available from this technology.
For this reason, there is an urgent need in the art to develop a method for preparing 1-methylcyclohexyl methacrylate with high yield and high product purity.
Disclosure of Invention
The present application aims to provide a method for preparing 1-methylcyclohexyl methacrylate with high yield and high product purity, which solves the above technical problems in the prior art. The process described herein allows high purity 1-methylcyclohexyl methacrylate to be obtained in high yield by reacting 1-methylcyclohexanol and methacryloyl chloride in the presence of a specific catalyst mixture.
In order to solve the above technical problems, the present application provides the following technical solutions.
In a first aspect, the present application provides a process for the preparation of 1-methylcyclohexyl methacrylate, characterized in that the process comprises the steps of:
s1: under the protection of inert gas and in the presence of at least a first catalyst, a second catalyst and a polymerization inhibitor, reacting 1-methylcyclohexanol with methacryloyl chloride in an organic solvent for a predetermined period of time to obtain a reaction mixture containing 1-methylcyclohexyl methacrylate;
s2: adding a predetermined weight of water into the first reaction mixture, demixing to obtain a first water phase and a first organic phase, then adding a predetermined weight of acid solution into the first organic phase, demixing to obtain a second water phase and a second organic phase, then adding a predetermined weight of water into the second organic phase, demixing to obtain a third water phase and a third organic phase, then adding an alkaline solution into the third organic phase, adjusting the pH value of the third organic phase to be more than 10, and demixing to obtain a fourth water phase and a fourth organic phase;
s3: and drying, concentrating and rectifying the fourth organic phase under reduced pressure, and collecting main fraction after the temperature is stabilized at about 68 ℃ for 5 minutes to obtain colorless transparent liquid 1-methyl cyclohexyl methacrylate.
In one embodiment of the first aspect, the first catalyst comprises a linear alkyl amine; and/or, the second catalyst comprises an aromatic amine.
In one embodiment of the first aspect, the linear alkyl amine comprises diethylamine and/or triethylamine; and/or, the aromatic amine comprises 4-dimethylaminopyridine.
In one embodiment of the first aspect, the second catalyst comprises less than or equal to 5% of the first catalyst on a weight basis.
In one embodiment of the first aspect, the polymerization inhibitor is one or more of p-methoxyphenol, hydroquinone, or phenothiazine.
In one embodiment of the first aspect, the organic solvent comprises dichloromethane.
In one embodiment of the first aspect, in step S2, the acid solution includes 6% by weight hydrochloric acid solution.
In one embodiment of the first aspect, in step S2, the alkaline solution comprises an aqueous solution of an alkali metal hydroxide and/or an aqueous solution of an alkaline earth metal hydroxide.
In one embodiment of the first aspect, in step S2, the content of impurities in the fourth organic phase is controlled to be less than 0.2% at a retention time of 5.5min as determined by GC.
In one embodiment of the first aspect, the 1-methylcyclohexanol is prepared by a process comprising: firstly, under the initiation of 1, 2-dibromoethane, methyl chloride reacts with metal magnesium to obtain a methyl chloride-based Grignard reagent; the methyl chloride-based Grignard reagent is then reacted with cyclohexanone in the presence of anhydrous lithium chloride to give the 1-methylcyclohexanol.
Compared with the prior art, the method has the beneficial effects that the reaction of the 1-methylcyclohexanol and the methacryloyl chloride is catalyzed by simultaneously adopting the linear alkylamine and the aromatic amine as the catalyst, so that the yield can be obviously improved, the impurity content is reduced, and the high-purity colorless transparent liquid 1-methylcyclohexyl methacrylate is finally obtained.
Detailed Description
Unless otherwise indicated, implied from the context, or customary in the art, all parts and percentages herein are by weight and the testing and characterization methods used are synchronized with the filing date of the present application. Where applicable, the contents of any patent, patent application, or publication referred to in this application are incorporated herein by reference in their entirety and their equivalent family patents are also incorporated by reference, especially as they disclose definitions relating to synthetic techniques, products and process designs, polymers, comonomers, initiators or catalysts, and the like, in the art. To the extent that a definition of a particular term disclosed in the prior art is inconsistent with any definitions provided herein, the definition of the term provided herein controls.
The numerical ranges in this application are approximations, and thus may include values outside of the ranges unless otherwise specified. A numerical range includes all numbers from the lower value to the upper value, in increments of 1 unit, provided that there is a separation of at least 2 units between any lower value and any higher value. For example, if a compositional, physical, or other property (e.g., molecular weight, melt index, etc.) is recited as 100 to 1000, it is intended that all individual values, e.g., 100, 101,102, etc., and all subranges, e.g., 100 to 166,155 to 170,198 to 200, etc., are explicitly recited. For ranges containing a numerical value less than 1 or containing a fraction greater than 1 (e.g., 1.1, 1.5, etc.), then 1 unit is considered appropriate to be 0.0001, 0.001, 0.01, or 0.1. For ranges containing single digit numbers less than 10 (e.g., 1 to 5), 1 unit is typically considered 0.1. these are merely specific examples of what is intended to be expressed and all possible combinations of numerical values between the lowest value and the highest value enumerated are to be considered to be expressly stated in this application.
When used with respect to chemical compounds, the singular includes all isomeric forms and vice versa (e.g., "hexane" includes all isomers of hexane, individually or collectively) unless expressly specified otherwise. In addition, unless explicitly stated otherwise, the use of the terms "a", "an" or "the" are intended to include the plural forms thereof.
The terms "comprising," "including," "having," and derivatives thereof do not exclude the presence of any other component, step or procedure, and are not intended to exclude the presence of other elements, steps or procedures not expressly disclosed herein. To the extent that any doubt is eliminated, all compositions herein containing, including, or having the term "comprise" may contain any additional additive, adjuvant, or compound, unless expressly stated otherwise. Rather, the term "consisting essentially of … …" excludes any other components, steps or processes from the scope of any of the terms hereinafter recited, except those necessary for performance. The term "consisting of … …" does not include any components, steps or processes not specifically described or listed. Unless explicitly stated otherwise, the term "or" refers to the listed individual members or any combination thereof.
Examples
The present application will be described in more detail with reference to examples.
Example 1
This example relates to the synthesis of 1-methylcyclohexyl methacrylate, the synthetic route of which is shown below:
the specific experimental procedures of this example are as follows.
The first step is as follows:
THF (800g) was added into a 2L four-necked reaction flask, the internal temperature was lowered to 0 ℃ by a dry ice bath of ethanol, and methyl chloride (200g) was introduced under control of 0 ℃ for 2 hours, and the solution was used after dropwise addition.
Magnesium chips (55.9g) and THF (80g) are added into a 5L four-mouth reaction bottle, nitrogen is introduced for protection, the internal temperature is raised to 60 ℃,1, 2-dibromoethane is added into drops for initiation, a large amount of bubbles appear in the reaction bottle, heat is rapidly released, reflux occurs, and the reaction liquid turns grey and finally becomes black. Cooling to 35 ℃, keeping the temperature of the system stable at 35 +/-5 ℃, and dropwise adding a methyl chloride THF solution for about 1 hour.
Then the system was cooled to 0 ℃,15 g of anhydrous lithium chloride was added, the dropwise addition of cyclohexanone (150g) was started, the dropwise addition temperature was controlled at 0 ± 5 ℃, the reaction liquid was initially black, and then slowly grayed and thickened. After the dripping is finished for 30 minutes, the temperature is raised to 10 +/-5 ℃, the temperature is kept at 10 +/-5 ℃ for reaction for 1 hour (the central control is 1, the GC detection shows that the content of the raw materials is less than 1 percent), and the central control result is qualified. A25% ammonium chloride aqueous solution was prepared, and water (245.5g) was added to ammonium chloride (81.8g) and the mixture was stirred until a clear solution was obtained. Dropping ammonium chloride solution at temperature below 20 deg.c. A white solid appeared in the reaction flask and was filtered off with suction. The filter cake was slurried twice with 225g of ethyl acetate each time and rinsed with 25g of ethyl acetate, the organic phases were combined and dried over anhydrous sodium sulfate. Concentration at 30 ℃ under reduced pressure gave 138g (control 2, GC < 5% in the residue).
Distilling by using a water pump, carrying out oil bath at 90 ℃, and beginning to produce front distillate at the top temperature of 74-78 ℃. After the top temperature is stabilized at 78 ℃ for 5 minutes, the main fraction is connected to obtain 115g of 1-methylcyclohexanol and colorless transparent liquid (the center is controlled to be 3, and the purity of the main content GC is more than 98%).
The second step is that:
dichloromethane (994g), 1-methylcyclohexanol (150g), triethylamine (332.3g), phenothiazine (1.5g) and DMAP (4-dimethylaminopyridine) (1.5g) were charged into a 2L four-necked flask at 25 ℃ under a nitrogen atmosphere. Cooling to 5 ℃, controlling the temperature to be 5 +/-5 ℃, dropwise adding methacryloyl chloride (206g) into the reaction bottle, wherein a large amount of white mist appears in the reaction bottle when dropwise adding, the reaction solution gradually changes from light green to yellow, a large amount of solid is separated out at the same time, and the dropwise adding is finished within about 1 hour. Heating to 15 +/-5 ℃, and reacting for 2 hours under the condition of heat preservation (the central control is 1, and the GC content of the raw material is less than 1%).
After the reaction is finished, 350g of water is added dropwise to the mixture to be quenched at the temperature of below 20 ℃, the mixture is stirred for 15min, and then layering is carried out. And (3) treating the upper water layer by using waste liquid, adding a 6% hydrochloric acid solution (85g of 36% hydrochloric acid and 415g of water) into the lower organic layer, adjusting the pH value to 6-7, stirring for 15min, layering, and treating the upper water layer by using waste acid. The lower organic layer was stirred with 350g of water for 15min and the layers were separated. Adding 2% sodium hydroxide solution (7g NaOH 343g water) into the lower organic layer, controlling the temperature below 20 deg.C, adding sodium hydroxide solution to adjust pH to be more than 10, layering, sampling GC from the lower organic layer (center control 2, impurity content is less than 0.2% at retention time 5.5 min), and repeating alkali washing until qualified if unqualified. The lower organic phase was dried by adding 30g of anhydrous sodium sulfate, and the sample was taken for moisture measurement (control 3, moisture < 0.5%).
And (3) transferring the organic phase to a 2L single-neck bottle, adding 0.1g of phenothiazine, controlling the water bath temperature to be 25-30 ℃, and concentrating to obtain 239.3 g of light yellow liquid (the control is 4, and the GC content of the dissolved residue is less than 5%).
The crude product was transferred to a 500mL single-neck flask and supplemented with 0.1g phenothiazine, and rectified under reduced pressure using a 20cm glass spring packed column. When the temperature of the oil bath is 90 ℃ and the top temperature is 64-68 ℃, the front fraction is extracted. After the temperature is stabilized at about 68 ℃ for 5 minutes, the main fraction is connected to obtain 190g of 1-methylcyclohexyl methacrylate, colorless transparent liquid with the molar yield of 85.6 percent (the central control is 5, and the GC purity of the product is more than 99 percent).
The embodiments described above are intended to facilitate the understanding and appreciation of the application by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present application is not limited to the embodiments herein, and those skilled in the art who have the benefit of this disclosure will appreciate that many modifications and variations are possible within the scope of the present application without departing from the scope and spirit of the present application.
Claims (5)
1. A method for preparing 1-methylcyclohexyl methacrylate, the method comprising the steps of:
s1: under the protection of inert gas and in the presence of at least a first catalyst, a second catalyst and a polymerization inhibitor, reacting 1-methylcyclohexanol with methacryloyl chloride in an organic solvent for a predetermined period of time to obtain a reaction mixture containing 1-methylcyclohexyl methacrylate; the catalyst comprises a first catalyst, a second catalyst and a polymerization inhibitor, wherein the first catalyst comprises diethylamine and/or triethylamine, the second catalyst comprises 4-dimethylaminopyridine, the proportion of the second catalyst in the first catalyst is less than or equal to 5% by weight, and the polymerization inhibitor is one or more of p-methoxyphenol, hydroquinone or phenothiazine;
s2: adding a predetermined weight of water into the first reaction mixture, demixing to obtain a first water phase and a first organic phase, then adding a predetermined weight of acid solution into the first organic phase, demixing to obtain a second water phase and a second organic phase, then adding a predetermined weight of water into the second organic phase, demixing to obtain a third water phase and a third organic phase, then adding an alkaline solution into the third organic phase, adjusting the pH value of the third organic phase to be more than 10, and demixing to obtain a fourth water phase and a fourth organic phase;
s3: and (3) drying, concentrating and rectifying the fourth organic phase under reduced pressure, and collecting a main fraction after the temperature is stabilized at 68 ℃ for 5 minutes to obtain colorless transparent liquid 1-methyl cyclohexyl methacrylate.
2. The method of claim 1, wherein the organic solvent comprises methylene chloride.
3. The method of preparing 1-methylcyclohexyl methacrylate as claimed in claim 1, wherein in step S2, the acid solution includes a 6% by weight hydrochloric acid solution.
4. The method of producing 1-methylcyclohexyl methacrylate as claimed in claim 1, wherein in step S2, the alkaline solution includes an aqueous solution of an alkali metal hydroxide and/or an aqueous solution of an alkaline earth metal hydroxide.
5. The process for preparing 1-methylcyclohexyl methacrylate according to claim 1, wherein the 1-methylcyclohexanol is prepared by: firstly, under the initiation of 1, 2-dibromoethane, methyl chloride reacts with metal magnesium to obtain a methyl chloride-based Grignard reagent; the methyl chloride-based Grignard reagent is then reacted with cyclohexanone in the presence of anhydrous lithium chloride to give the 1-methylcyclohexanol.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001354605A (en) * | 2000-06-09 | 2001-12-25 | Idemitsu Petrochem Co Ltd | Method for manufacturing tertiary alcohol |
| JP2008268743A (en) * | 2007-04-24 | 2008-11-06 | Fujifilm Corp | Positive photosensitive composition and pattern forming method using the same |
| CN104910012A (en) * | 2015-05-19 | 2015-09-16 | 中节能万润股份有限公司 | Method for preparing 1-ethylcyclohexyl acrylate |
| JP2016050296A (en) * | 2014-09-02 | 2016-04-11 | 学校法人慶應義塾 | Fluorochrome-coupled coelenterazine |
| CN108264605A (en) * | 2016-12-30 | 2018-07-10 | 罗门哈斯电子材料韩国有限公司 | Monomer, polymer and photo-corrosion-resisting agent composition |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001354605A (en) * | 2000-06-09 | 2001-12-25 | Idemitsu Petrochem Co Ltd | Method for manufacturing tertiary alcohol |
| JP2008268743A (en) * | 2007-04-24 | 2008-11-06 | Fujifilm Corp | Positive photosensitive composition and pattern forming method using the same |
| JP2016050296A (en) * | 2014-09-02 | 2016-04-11 | 学校法人慶應義塾 | Fluorochrome-coupled coelenterazine |
| CN104910012A (en) * | 2015-05-19 | 2015-09-16 | 中节能万润股份有限公司 | Method for preparing 1-ethylcyclohexyl acrylate |
| CN108264605A (en) * | 2016-12-30 | 2018-07-10 | 罗门哈斯电子材料韩国有限公司 | Monomer, polymer and photo-corrosion-resisting agent composition |
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