CN109485565A - A kind of preparation method of 1- methylcyclohexylmethyl acrylate - Google Patents
A kind of preparation method of 1- methylcyclohexylmethyl acrylate Download PDFInfo
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- CN109485565A CN109485565A CN201811380776.5A CN201811380776A CN109485565A CN 109485565 A CN109485565 A CN 109485565A CN 201811380776 A CN201811380776 A CN 201811380776A CN 109485565 A CN109485565 A CN 109485565A
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- methylcyclohexylmethyl
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- acrylate
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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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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
This application involves a kind of preparation methods of 1- methylcyclohexylmethyl acrylate; it is the following steps are included: S1: under inert gas protection; and in the case where there is at least the first catalyst, the second catalyst and polymerization inhibitor; it reacts 1 methyl cyclohexanol in organic solvent with methacrylic chloride, obtains the reaction mixture of the acrylate of methylcyclohexylmethyl containing 1-；S2: successively using water, the first reaction mixture of acid solution, water and alkaline wash, and layering obtains the 4th water phase and the 4th organic phase；S3: being dried the 4th organic phase, be concentrated and rectification under vacuum, when temperature is stablized at 68 DEG C or so after five minutes, collects main distillate fraction, obtains colourless transparent liquid 1- methylcyclohexylmethyl acrylate.The beneficial effects of the present application are as follows simultaneously using straight chain alkyl amine and aromatic amine as the catalyst to the reaction of catalysis 1 methyl cyclohexanol and methacrylic chloride, can significantly improve product yield, the impurity content in reduction product.
Description
Technical field
This application involves organic chemical synthesis technical fields.Specifically, this application involves a kind of 1- methylcyclohexyl first
The preparation method of base acrylate.
Background technique
Polymethacrylate is the matrix resin of 193nm photoresist, and film-forming resin main component is birdsed of the same feather flock together for alicyclic ring
Close object.The main chain of esters of acrylic acid photoresist film-forming resin is generally the condensate of methylene, and main function is to provide film forming
With the required mechanical performance of process, and its at image force, adhesiveness, can developability and most corrosion stability by side
Chain undertakes.Therefore, the side chain design of matrix resin is particularly critical.
Since linear structure (low C/H ratio) resistance to dry etching of its main chain is poor, to meet this requirement, 193nm is designed
It is generallyd use when the film-forming resin of photoresist and introduces big fat group in the side chain, such as hexamethylene, lauryl, adamantane
Base etc. forms an effective, balance controllable part so as to control the penetration power and dispersion force of organic base.Simultaneously in side chain
Ring-type on be further introduced into methyl, its corrosion stability and adhesiveness can be improved, to provide a kind of chemical resistance excellent photosensitive
Property resin monomer.
It is related to the synthesis of 1- cyclohexyl methyl acrylate in patent JPWO2016125782A1, the existing patent
In directly adopt the pure and mild methacrylic chloride of 1- cyclohexyl and react 1- cyclohexyl methyl acrylate is made.It synthesizes road
Line is as follows:
Synthesis in the prior art in relation to 1- cyclohexyl methyl acrylate is that directly adopt 1- cyclohexyl pure and mild
Methacrylic chloride reaction is made.Other 1 alkyl-substituted cyclohexyl methyl propylene can not be directly obtained from the technology
The preparation method of acid esters.
For this purpose, there is an urgent need in the art to develop a kind of high income and the high 1- methylcyclohexylmethyl acrylic acid of product purity
The preparation method of ester.
Summary of the invention
The application's is designed to provide a kind of high income and the high 1- methylcyclohexylmethyl acrylate of product purity
Preparation method, come solve it is above-mentioned in the prior art the technical issues of.Method described herein by make 1 methyl cyclohexanol and
Methacrylic chloride reacts in the case of there are special catalyst mixture, can obtain high-purity 1- methyl cyclohexane in high yield
Methyl acrylate.
In order to solve the above-mentioned technical problem, the application provides following technical proposals.
In the first aspect, the application provides a kind of preparation method of 1- methylcyclohexylmethyl acrylate, feature
It is, the described method comprises the following steps:
S1: under inert gas protection, and in there is at least the first catalyst, the second catalyst and the case where polymerization inhibitor
Under, so that 1 methyl cyclohexanol is reacted predetermined amount of time in organic solvent with methacrylic chloride, obtains methylcyclohexyl containing 1-
The reaction mixture of methacrylate；
S2: the water of predetermined weight being added into the first reaction mixture, and layering obtains the first water phase and the first organic phase, so
The acid solution of predetermined weight is added into the first organic phase again afterwards, layering obtains the second water phase and Second Organic Phase, then again
The water of predetermined weight is added into Second Organic Phase, layering obtains third water phase and third organic phase, next organic to third
Alkaline solution is added in phase, the pH value of third organic phase is adjusted to being greater than 10, and layering obtains the 4th water phase and the 4th organic
Phase；
S3: being dried the 4th organic phase, be concentrated and rectification under vacuum, when temperature is stablized at 68 DEG C or so after five minutes, receives
Collect main distillate fraction, obtains colourless transparent liquid 1- methylcyclohexylmethyl acrylate.
In a kind of embodiment of first aspect, first catalyst includes straight chain alkyl amine；And/or described
Two catalyst include aromatic amine.
In a kind of embodiment of first aspect, the straight chain alkyl amine includes diethylamine and/or triethylamine；And/or
The aromatic amine includes 4-dimethylaminopyridine.
In a kind of embodiment of first aspect, remembered on the basis of weight, second catalyst accounts for institute first and is catalyzed
Agent is less than or equal to 5%.
In a kind of embodiment of first aspect, the polymerization inhibitor is p methoxy phenol, hydroquinone or phenthazine
One or more of.
In a kind of embodiment of first aspect, the organic solvent includes methylene chloride.
In a kind of embodiment of first aspect, in step s 2, the acid solution includes the salt that weight fraction is 6%
Acid solution.
In a kind of embodiment of first aspect, in step s 2, the alkaline solution includes alkali metal hydroxide
Aqueous solution and/or alkaline earth metal hydroxide aqueous solution.
In a kind of embodiment of first aspect, in step s 2, controls in the 4th organic phase and protected by GC measurement
Staying the time is the impurity content at 5.5min less than 0.2%.
In a kind of embodiment of first aspect, the 1 methyl cyclohexanol is prepared by following methods: being existed first
It under the initiation of 1,2- Bromofume, reacts chloromethanes with magnesium metal, obtains the grignard reagent based on chloromethanes；Then, it is depositing
In the case where anhydrous lithium chloride, makes the grignard reagent and hexamethylene reactive ketone based on chloromethanes, obtain the 1- methyl ring
Hexanol.
Compared with prior art, it is urged the beneficial effects of the present application are as follows being used as simultaneously using straight chain alkyl amine and aromatic amine
Agent is catalyzed the reaction of 1 methyl cyclohexanol and methacrylic chloride, can significantly improve yield, reduces impurity content, finally
Obtain the colourless transparent liquid shape 1- methylcyclohexylmethyl acrylate of high-purity.
Specific embodiment
Unless otherwise indicated, from context cues or belong to the convention of the prior art, otherwise number all in the application
It is all based on weight with percentage, and test and characterizing method used is all synchronous with the submission date of the application.It is being applicable in
In the case where, any patent, patent application or disclosure involved in the application are fully incorporated in this as reference, and its
Patent families of equal value are also introduced into as reference, about the synthetic technology in this field, product disclosed by these special documents
With the definition of fabrication design, polymer, comonomer, initiator or catalyst etc..If the specific art disclosed in the prior art
Defining for language is inconsistent with any definition provided herein, then term provided herein of being subject to defines.
Digital scope in the application is approximation, therefore unless otherwise stated, it may include the number other than range
Value.Numberical range include with the increased all numerical value from lower limit value to upper limit value of 1 unit, condition be any lower value with
There are the intervals of at least two unit between any high value.For example, if compositional, physics or other property (such as molecules
Amount, melt index (MI) etc.) it is 100 to 1000, it is meant that clearly list all single numbers, such as 100,101,102 etc., with
And all subranges, such as 100 to 166,155 to 170,198 to 200 etc..For comprising the numerical value less than 1 or comprising big
In the range of 1 score (such as 1.1,1.5 etc.), then suitably regard 1 unit as 0.0001,0.001,0.01 or 0.1.
For the range comprising the units less than 10 (such as 1 to 5), usually regarding 1 unit as 0.1., these are only intended to table
The specific example of the content reached, and all possible combination of the numerical value between cited minimum and peak is all recognized
In this application for clear record.
About chemical compound in use, unless explicitly stated otherwise, otherwise odd number includes all isomeric forms, otherwise also
So (for example, whole isomers that " hexane " either individually or collectively includes hexane).In addition, unless explicitly stated otherwise, otherwise using
"one", the noun that "an" or "the" are described also includes its plural form.
Term "comprising", " comprising ", " having " and their derivative are not excluded for any other component, step or mistake
The presence of journey, and whether disclose in this application with these other components, step or process unrelated.To eliminate any query,
Unless expressly stated, otherwise in the application it is all use term "comprising"s, " comprising ", or " having " composition may include appoint
What additional additive, auxiliary material or compound.On the contrary, in addition to necessary to operating characteristics those, term " substantially by ...
Composition " excludes any other component, step or process except the hereinafter described range of any term.Term " by ...
Composition " does not include any component, step or the process for not specifically describing or listing.Unless expressly stated, otherwise term "or" refers to
Separate member listed or any combination thereof.
Embodiment
Below in conjunction with embodiment, the application is described in more details.
Embodiment 1
The present embodiment is related to synthesizing 1- methylcyclohexylmethyl acrylate, and synthetic route is as follows:
That steps are as follows is described for the specific experiment of the present embodiment.
Step 1:
Into four mouthfuls of reaction flasks of 2L be added THF (800g), by ethyl alcohol the dry ice bath by interior temperature drop to 0 DEG C, control 0 DEG C with
Logical chloromethanes (200g) down, is added dropwise, solution for later use for 2 hours.
Magnesium chips (55.9g) and THF (80g) are added in tetra- mouthfuls of reaction flasks of 5L, nitrogen protection is led to, interior temperature is warming up to 60 DEG C,
Drops adds 1,2- Bromofume to cause, and a large amount of bubbles occurs in reaction flask, sharply heat release flows back, and reaction solution is graying, finally
In black.35 DEG C are cooled to, system temperature is kept to stablize at 35 DEG C ± 5 DEG C, the THF solution of chloromethanes is added dropwise, is dripped within about 1 hour
It is complete.
Then system is cooled to 0 DEG C, 15g anhydrous lithium chloride is added, start that cyclohexanone (150g) is added dropwise, dropping temperature control
System is in 0 ± 5 DEG C, and reaction solution is black when beginning, after it is slowly graying and become sticky.It is added dropwise within 30 minutes, is warming up to 10 ± 5
DEG C, kept for 10 ± 5 DEG C react 1 hour (1, GC of middle control detection, material content < 1%), middle control result is qualified.Configure 25% chlorination
Aqueous ammonium, ammonium chloride (81.8g) are added water (245.5g) and stir to clarify liquid.Aqueous ammonium chloride solution is added dropwise, temperature control exists
20 DEG C or less.Occur white solid in reaction flask, filters.Filter cake uses the mashing of 225g ethyl acetate twice every time, and with 25g acetic acid
Ethyl ester elution, merges organic phase, and it is dry that anhydrous sodium sulfate is added.30 DEG C reduced pressure, obtain weak yellow liquid 138g (it is middle control 2,
Molten residual GC < 5%).
It is distilled using water pump, 90 DEG C of oil bath, 74~78 DEG C of top temperature starts front-end volatiles out.When pushing up warm 78 DEG C of stabilizations after five minutes,
Main distillate fraction is connect, 1 methyl cyclohexanol 115g, colourless transparent liquid (middle control 3, main content GC purity > 98%) are obtained.
Step 2:
Under nitrogen protection, methylene chloride (994g) is added into 2L four-hole bottle at 25 DEG C, 1 methyl cyclohexanol (150g),
Triethylamine (332.3g), phenthazine (1.5g), DMAP (4-dimethylaminopyridine) (1.5g).5 DEG C are cooled to, temperature 5 ± 5 is controlled
DEG C, methacrylic chloride (206g) is added dropwise into reaction flask, when dropwise addition, a large amount of white hazes are appeared in reaction flask, and reaction solution is gradually
Become yellow from light green color, while a large amount of solids are precipitated, is added dropwise within about 1 hour.15 ± 5 DEG C are warming up to, insulation reaction 2 is small
When, (middle control 1, material content GC < 1%).
After completion of the reaction, it keeps 20 DEG C of temperature or less 350g water quenching is added dropwise to go out, stirs 15min, layering.Upper aqueous layer is cancelled
Liquid processing, lower organic layer add 6% hydrochloric acid solution (36% hydrochloric acid of 85g, 415g water), adjust pH=6~7, stir 15min, point
Layer, upper aqueous layer make waste acid treatment.Lower organic layer adds 350g water to stir 15min, layering.Lower organic layer adds 2% hydroxide
Sodium solution (7g NaOH 343g water), control temperature adjust pH > 10, layering, lower layer in 20 DEG C or less addition sodium hydroxide solutions
Organic layer samples GC (middle to control 2, impurity content < 0.2% at retention time 5.5min), if unqualified, repeatedly alkali cleaning is until close
Lattice.The organic 30g anhydrous sodium sulfate that is added to of lower layer is dry, and moisture (middle control 3, moisture < 0.5%) is surveyed in sampling.
Organic phase is transferred to addition 0.1g phenthazine in 2L single port bottle, controls bath temperature at 25~30 DEG C, concentration
Obtain 239.3.g weak yellow liquid (middle control 4, molten residual GC < 5%).
Crude product is transferred in 500mL single port bottle and adds 0.1g phenthazine, with 20cm glass spring filled column rectification under vacuum.
At 90 DEG C of oil bath, top is warm at 64-68 DEG C, out front-end volatiles.When temperature stablize at 68 DEG C or so after five minutes, connect main distillate fraction, obtain
1- methylcyclohexylmethyl acrylate 190g, colourless transparent liquid, molar yield 85.6% (middle control 5, product GC purity >
99%).
The above-mentioned description to embodiment is that this Shen can be understood and applied for the ease of those skilled in the art
Please.Person skilled in the art obviously easily can make various modifications to these embodiments, and described herein
General Principle is applied in other embodiments without paying creative labor.Therefore, the application is not limited to implementation here
Example, those skilled in the art make according to herein disclosed content in the case where not departing from the application scope and spirit
It improves and modifies within all scope of the present application.
Claims (10)
1. a kind of preparation method of 1- methylcyclohexylmethyl acrylate, which is characterized in that the described method comprises the following steps:
S1: under inert gas protection, and in the case where there is at least the first catalyst, the second catalyst and polymerization inhibitor, make
1 methyl cyclohexanol reacts predetermined amount of time with methacrylic chloride in organic solvent, obtains methylcyclohexylmethyl containing 1- third
The reaction mixture of olefin(e) acid ester；
S2: the water of predetermined weight being added into the first reaction mixture, and layering obtains the first water phase and the first organic phase, then again
The acid solution of predetermined weight is added into the first organic phase, layering obtains the second water phase and Second Organic Phase, then again to the
The water of predetermined weight is added in two organic phases, layering obtains third water phase and third organic phase, next into third organic phase
Alkaline solution is added, the pH value of third organic phase is adjusted and is arrived greater than 10, and layering obtains the 4th water phase and the 4th organic phase；
S3: being dried the 4th organic phase, be concentrated and rectification under vacuum, when temperature is stablized at 68 DEG C or so after five minutes, collects master
Fraction obtains colourless transparent liquid 1- methylcyclohexylmethyl acrylate.
2. the preparation method of 1- methylcyclohexylmethyl acrylate as described in claim 1, which is characterized in that described first
Catalyst includes straight chain alkyl amine；And/or second catalyst includes aromatic amine.
3. the preparation method of 1- methylcyclohexylmethyl acrylate as claimed in claim 2, which is characterized in that the straight chain
Alkylamine includes diethylamine and/or triethylamine；And/or the aromatic amine includes 4-dimethylaminopyridine.
4. the preparation method of 1- methylcyclohexylmethyl acrylate as described in claim 1, which is characterized in that be with weight
Benchmark note, second catalyst account for the first catalyst of institute less than or equal to 5%.
5. the preparation method of 1- methylcyclohexylmethyl acrylate as described in claim 1, which is characterized in that the polymerization inhibitor
Agent is one or more of p methoxy phenol, hydroquinone or phenthazine.
6. the preparation method of 1- methylcyclohexylmethyl acrylate as described in claim 1, which is characterized in that described organic
Solvent includes methylene chloride.
7. the preparation method of 1- methylcyclohexylmethyl acrylate as described in claim 1, which is characterized in that in step S2
In, the acid solution includes the hydrochloric acid solution that weight fraction is 6%.
8. the preparation method of 1- methylcyclohexylmethyl acrylate as described in claim 1, which is characterized in that in step S2
In, the alkaline solution includes the aqueous solution of alkali metal hydroxide and/or the aqueous solution of alkaline earth metal hydroxide.
9. the preparation method of 1- methylcyclohexylmethyl acrylate as described in claim 1, which is characterized in that in step S2
In, being measured by GC in retention time in the 4th organic phase of control is the impurity content at 5.5min less than 0.2%.
10. the preparation method of 1- methylcyclohexylmethyl acrylate as described in claim 1, which is characterized in that the 1-
Methyl cyclohexanol is prepared by following methods: first under the initiation of 1,2- Bromofume, react chloromethanes with magnesium metal,
Obtain the grignard reagent based on chloromethanes；Then, there are anhydrous lithium chloride, make the format based on chloromethanes
Reagent and hexamethylene reactive ketone, obtain the 1 methyl cyclohexanol.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201811380776.5A CN109485565B (en) | 2018-11-20 | 2018-11-20 | Preparation method of 1-methyl cyclohexyl methacrylate |
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| CN201811380776.5A CN109485565B (en) | 2018-11-20 | 2018-11-20 | Preparation method of 1-methyl cyclohexyl methacrylate |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114276242A (en) * | 2021-12-30 | 2022-04-05 | 徐州博康信息化学品有限公司 | Preparation method of acid-sensitive photoresist resin monomer |
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| 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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| 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 |
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| 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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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114276242A (en) * | 2021-12-30 | 2022-04-05 | 徐州博康信息化学品有限公司 | Preparation method of acid-sensitive photoresist resin monomer |
| CN114276242B (en) * | 2021-12-30 | 2023-12-29 | 徐州博康信息化学品有限公司 | Preparation method of acid-sensitive photoresist resin monomer |
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