CN104628561B - Preparation method for 2-ethyl-2-adamantanol methacrylate - Google Patents
Preparation method for 2-ethyl-2-adamantanol methacrylate Download PDFInfo
- Publication number
- CN104628561B CN104628561B CN201310557438.5A CN201310557438A CN104628561B CN 104628561 B CN104628561 B CN 104628561B CN 201310557438 A CN201310557438 A CN 201310557438A CN 104628561 B CN104628561 B CN 104628561B
- Authority
- CN
- China
- Prior art keywords
- reaction
- hours
- stirring
- organic layer
- drip
- 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
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/14—Preparation of carboxylic acid esters from carboxylic acid halides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2603/00—Systems containing at least three condensed rings
- C07C2603/56—Ring systems containing bridged rings
- C07C2603/58—Ring systems containing bridged rings containing three rings
- C07C2603/70—Ring systems containing bridged rings containing three rings containing only six-membered rings
- C07C2603/74—Adamantanes
Abstract
The invention provides a preparation method for 2-ethyl-2-adamantanol methacrylate. The method is characterized by including the steps of: adding bromoethane into adamantanone of a solvent dropwise to form a No.1 preparatory solution; placing a metal into the solvent to form a No.2 preparatory solution; adding the No.1 preparatory solution into the No.2 preparatory solution slowly in a dropwise manner; raising the temperature to room temperature naturally and carrying out reaction for 10-20h; under a system temperature below 0DEG C, adding a polymerization inhibitor, and adding methacryloyl chloride dropwise; raising the temperature to room temperature naturally and carrying out reaction for 10-20h; adding water to carry out quenching reaction; and performing aftertreatment to obtain 2-ethyl-2-adamantanol methacrylate. According to the synthesis method provided by the invention, by selecting the reaction conditions of each step, like reaction temperature, reactant ratio, reaction time, reaction feedstock and the like, the problems of difficult purification, too high cost, low reaction yield, low product purity, inapplicability to large-scale industrial production and the like in existing technical disclosure can be overcome.
Description
Technical field
The present invention relates to organic synthesis field, specifically provides a kind of 2- ethyls -2- adamantanol methacrylates
Preparation method.
Background technology
Diamantane (obsolete), is a kind of straight, symmetrical, high stability caged hydrocarbon, because being condensed into cage with four cyclohexane rings
The structure of shape, therefore, it is a kind of high and stable compound of symmetry.Known its derivant is related to medicine, Aero-Space, function
The fields such as material, PETROLEUM PROCESSING.
It is noted that because diamantane (obsolete) has such as property such as optical characteristics, thermostability, therefore, its derivant is normal
In being used for optic disc base board, optical fiber or lens lamp.Can be used as quasiconductor photoresist, photosemiconductor sealant, optics
Electronic unit (light guide, optic communication lens and optical thin film etc.) and their bonding agent.
Wherein, the electronic component for being manufactured as raw material using alkyl adamantane esters of acrylic acid, in semiconductor fabrication process
In dry etching patience it is high, it is wide as the development prospect of quasiconductor material.
The alkyl Buddha's warrior attendant alkyl ester obtained using known method of the prior art is often due to side reaction is excessively produced in a large number
Impurity, cause separation process complicated, it is impossible to obtain pure products by modes such as crystallizations, and then cause yield low, cost is difficult
To control, it is also directly caused not to be readily applied to industrial production.
The content of the invention
It is contemplated that overcoming drawbacks described above, there is provided a kind of high yield, high-purity, environmental protection, it is cheap, industry can be carried out
The preparation method of the 2- ethyl -2- adamantanol methacrylates of production.
For achieving the above object, the preparation method of 2- ethyls -2- adamantanol methacrylates according to the present invention, its
It is characterised by, comprises the following steps：
Step one, by bromoethane Deca in being dissolved in the Buddha's warrior attendant alkanone of solvent, form preparation liquid one；
In the present invention, it is general that bromoethane is added in the case of stirring from Buddha's warrior attendant alkanone is dissolved in solvent, protect
Stir molten clear stand-by to whole under the protection of gas.
In the present invention, above-mentioned solvent may be selected from anhydrous tetrahydro furan, Anaesthetie Ether, toluene, benzene, alkane, anhydrous benzene
The mixture of one or more.
Shielding gas may be selected from the noble gases such as nitrogen, argon, helium.
Additionally, Buddha's warrior attendant alkanone is 1 with the mol ratio of bromoethane:1.1-1.8.Preferably 1:1.4-1.8.
Diamantane (obsolete) is dissolved in the mass percent concentration after solvent for 20-50%, preferably 30-40%.It is anti-when the concentration is too high
Should be excessively violent；When the concentration is too low solute excessively disperses, and causes reaction incomplete.
In step 2, the solvent for being placed on metal, preparation liquid two is formed.
In the present invention, Buddha's warrior attendant alkanone and the mol ratio of lithium metal are 1:1.6-2.5.Preferably 1:2.1-2.5.
Metal can be the metals such as lithium metal, magnesium metal.
It is 1-30% that metal accounts for the mass percent concentration of solution, selects 10-20%.The concentration of metal is unsuitable too high, otherwise
Reaction can be caused excessively acutely, and produce substantial amounts of heat, so as to destroy the stability of reaction.
Solvent may be selected from the mixed of one or more in anhydrous tetrahydro furan, Anaesthetie Ether, toluene, benzene, alkane, anhydrous benzene
Compound.
Additionally, the high efficiency to ensure reaction, prepares and strictly to control during lithium reagent moisture and air, so the step
Suddenly it is also preferred that from protection gas shielded.
Step 3, preparation liquid one is slowly added dropwise into preparation liquid two.
It should be noted that the step is preferably from protection gas shielded.
In the present invention, the step should be during the temperature below 0 DEG C starts Deca, Deca, and temperature is preferably controlled
Between 10 DEG C -20 DEG C, the speed of Deca is preferably controlled in 0.1-1%/min, completion of dropping in about 5-10 hours to system.
0.5-2 hours are incubated after being added dropwise to complete.
Step 4, be warmed to room temperature naturally after, react 10-20 hours, preferred reaction time be 10-14 hours.
The judgement of above-mentioned reaction end is preferably adopted, take sample add water be quenched reaction after, TLC combine GC detection pattern.
Step 5, less than 0 DEG C is cooled to, is preferably cooled to less than -5 DEG C, add poly- resist.
Poly- resist may be selected from one or more in phenolic inhibitor, quinones polymerization inhibitor, arene nitro compound polymerization inhibitor
Compositionss.
The quality of poly- resist is the 0.1-10%, preferably 0.5-1.5% of the quality of Buddha's warrior attendant alkanone.
Step 6, Deca methacrylic chloride；
Buddha's warrior attendant alkanone is 1 with the mol ratio of methacrylic chloride:1.0-1.6.Preferably 1:1.2-1.6.
It should be noted that the speed of Deca methacrylic chloride should with by system temperature control -10 DEG C～-5
It is advisable between DEG C, 0.5-1.5 hour is incubated after being added dropwise to complete and is advisable.
Step 7, be warmed to room temperature naturally after, react 10-20 hours, preferred reaction time be 10-14 hours.
The judgement of above-mentioned reaction end is preferably adopted, take sample add water be quenched reaction after, with TLC examination whether there is raw material
It is defined.
Step 8, reaction add water after terminating and reaction are quenched.
The usage amount of water is 0.1-5 times of Buddha's warrior attendant alkanone quality.
Additionally, this adds water, the process that is quenched should be carried out in ice bath, and the speed of Deca water should be with by the temperature of reaction system
Degree control is advisable within 20 DEG C.
Step 9, post-treated obtain 2- ethyl -2- adamantanol methacrylates.
Post processing in above-mentioned steps is extraction at least one times, crystallization at least one times and concentration at least one times.
Concrete step is：（1）After static layering, taking organic layer carries out vacuum distillation.
（2）After water layer is extracted at least one times with extract, merging organic layer carries out vacuum distillation.
（3）After with extract dilution, repeatedly neutralization washing is carried out with the alkali liquor after dilution.
（4）Repeatedly after washing, organic layer is taken, concentrated after silica gel is filtered.
（5）Ice bath crystallize is filtered, alcohol is washed to going out completely after crystalline substance.
（6）The yield that sterling is obtained after repeated recrystallize is 65-99%.
It is worthy of note that, solvent can not be completely evaporated during refinement mother liquor secondary recovery, steam to it is micro- dry when add alcohol beat
Reprocess after slurry, it is such as unqualified to be beaten with alcohol again.
Wherein, one or more of extract in alkane, ethers, cycloalkane, esters obtain mixture.
The consumption of silica gel is 0.1-10 times of Buddha's warrior attendant alkanone quality.
The quality of extract is 1-50 times, preferably 4-10 times of Buddha's warrior attendant alkanone.
The optional mass concentration of alkali liquor of neutralization is sodium hydroxide, potassium hydroxide, sodium bicarbonate of 5-15% etc..
The washed journey of alcohol may be selected from methanol, ethanol etc. from alcohol, and quality is 0.1-5 times of Buddha's warrior attendant alkanone.
Further, since product involved in the present invention is to hot very sensitive, vacuum distillation（Concentration）When temperature it is unsuitable high
20 DEG C are crossed, impurity is otherwise had（Such as：Alkene）Generate.
Concrete reaction equation is as follows：
In addition, can be replaced with any halogenated compound in bromoethane of the present invention, methacrylic chloride can be substituted
For any chloride compounds for replacing, for preparing the derivant of 2- Buddha's warrior attendant alkyl esters.
The effect of invention and effect
The present invention by protection gas shielded, low-temp reaction, the condition such as response time control obtain a kind of by-product it is few, point
The method for preparing 2- ethyl -2- adamantanol methacrylates simple from process, product purity is high, yield is high.
Empirical tests find that product prepared by the present invention is very sensitive to heat, to it requires and strictly to control temperature in reaction
Degree.For ensure product purity, improve product yield, the present invention advocate by reaction temperature, thickening temperature all should control 20 DEG C with
Under cryogenic conditions under carry out, so as to avoid impurity（Alkene）Generation.Additionally, impurity alkene is when generating in recrystallization,
Substantial amounts of product can be caused to lose, therefore the temperature of re-crystallization stage should also be as controlling below 20 DEG C.In addition, temperature during drying
No more than 25 DEG C, molten condition otherwise occurs so as to polymerization occur affects product quality and yield.
It is to ensure conversion rate of products in view of the said goods characteristic, further reduces production cost, after completion of the reaction
The stage of reaction is quenched, the speed of Deca water will be advisable with reacting liquid temperature less than 20 DEG C, otherwise might have impurity alkene life
Into.
The present invention also indicates that, prepares and strictly to control during lithium reagent moisture and air, so to be protected using shielding gas
The measure of shield.
Unaffected to ensure product yield, the present invention is also defined to the process of recrystallization.
The present invention also indicates that, due to product metal ion is required it is higher, so, in addition to it need to protect gas shielded, rear
Processing stage it is also preferred that from deionized water.
In sum, in the synthetic method that the present invention is provided, by the selection of each step reaction condition, such as：Reaction temperature,
Reaction ratio, response time, reaction raw materials etc., overcome during prior art discloses, purification difficult, high cost, reaction yield
Low, product purity is low, the problems such as be not suitable for large-scale industrial production.
Specific embodiment
Embodiment one,
Step one, 500g Buddha's warrior attendant alkanones are dissolved in 1550ml anhydrous tetrahydro furans, stirring is lower to add 500g bromoethanes, nitrogen
Stir molten clear stand-by to whole under gas shielded.
Step 2, by the lithium metal of 50g and 450ml anhydrous tetrahydro furans（Moisture is less than 200ppm）Add to band mechanical agitation
5000ml reaction bulbs in, be cooled to while stirring -5 DEG C～0 DEG C start the above-mentioned mixed solution of Deca drip off within about 7 hours, control
Temperature is at 10 DEG C～20 DEG C.
Step 3, drip off after insulation remove cooling system and be warmed to room temperature naturally after 1 hour（20 DEG C～25 DEG C）Stir about 14
Hour, sampling adds water and TLC after reaction is quenched, while after sample presentation GC detections are qualified（Middle control 1）.
Step 4, be cooled to -10 DEG C～-8 DEG C after add 5g phenothiazine start Deca 418g methacrylic chloride control
Rate of addition is by temperature control at -10 DEG C～-5 DEG C.
Step 5, drip off after insulation remove cooling system and be warmed to room temperature naturally after 1 hour（20 DEG C～25 DEG C）Stir about 14
Hour after sample sampling add water be quenched reaction after TLC without raw material point after（Middle control 2）, to Deca in 5000ml reaction bulbs under ice bath
400ml deionized waters are quenched reaction.
Step 6, reactant liquor is transferred to static 30min branch vibration layers after solution is distinguished in 5000ml separatory funnels, is had
Machine layer is transferred to when 20 DEG C of decompression steamings are reserved to no liquid on Rotary Evaporators and removes；
Water layer 500ml n-hexane extractioies twice, organic layer and will merge and be evaporated, and 1500ml is being added just in reactant liquor
Hexane dilution after with 800 × 2 10%（Mass ratio）NaOH is washed, and organic layer is gone again with after the deionized water wash of 800ml × 2 points
Water layer, organic layer is crossed after being rinsed with 1.5L normal hexane after silica gel, and 20 DEG C of mother solution is evaporated to no liquid and reserves；
Then will be equipped with the reaction bulb of concentrated solution and 0 DEG C of stirring and crystallizing sucking filtration, filter cake after 5 hours are cooled under ice bath stirring
Washed and starched with 200ml ice methanol after draining again with 100ml ice methanol drip washing, HPLC detections are sampled after draining qualified（Middle control 3）Filter cake
It is transferred to 20 DEG C～25 DEG C decompression dryings in drip pan and the about 510g of product 1 is obtained after 10 hours；
Filtrate is put to refrigerator and freezes 10 hours and have substantial amounts of faint yellow solid to separate out, filter cake 200ml methanol after sucking filtration
Use 50ml ice methanol drip washing after beating again, HPLC detections are sampled after draining qualified（Middle control 3）Post-drying obtains the about 175g of product 2, filter
Carry out unifying to refine with other batches after liquid concentration.
Embodiment two,
Step one, 150g Buddha's warrior attendant alkanones are dissolved in 370ml anhydrous benzene, stirring is lower to add 120g bromoethanes, nitrogen protection
Under stir to all molten clear stand-by.
Step 2, the magnesium metal of 38.4g and 190ml anhydrous benzene are added to in churned mechanically 1000ml reaction bulbs, side
Stirring side is cooled to -5 DEG C～0 DEG C beginning above-mentioned mixed solution of Deca and drips off for about 5 hours, and control temperature is at 10 DEG C～20 DEG C.
Step 3, drip off after insulation remove cooling system and be warmed to room temperature naturally after 1 hour（20 DEG C～25 DEG C）Stir about 12
Hour, sampling adds water and TLC after reaction is quenched, while after sample presentation GC detections are qualified（Middle control 1）.
Step 4, be cooled to -10 DEG C～-8 DEG C after add l, 4- naphthoquinone 4.5g to start Deca 166g methacrylic chloride
Control rate of addition is by temperature control at -10 DEG C～-5 DEG C.
Step 5, drip off after insulation remove cooling system and be warmed to room temperature naturally after 1 hour（20 DEG C～25 DEG C）Stir about 12
Hour after sample sampling add water be quenched reaction after TLC without raw material point after（Middle control 2）, to Deca in 1000ml reaction bulbs under ice bath
120ml deionized waters are quenched reaction.
Step 6, reactant liquor is transferred to static 30min branch vibration layers after solution is distinguished in 1000ml separatory funnels, is had
Machine layer is transferred to when 20 DEG C of decompression steamings are reserved to no liquid on Rotary Evaporators and removes；
Water layer is extracted twice with 100ml hexamethylene, organic layer and will be merged and is evaporated, and 300ml rings are added in reactant liquor
Hexane dilution after with 250 × 2 10%（Mass ratio）NaOH is washed, and organic layer is gone again with after the deionized water wash of 800ml × 2 points
Water layer, organic layer is crossed after being rinsed with 1.5L hexamethylene after silica gel, and 20 DEG C of mother solution is evaporated to no liquid and reserves；
Then will be equipped with the reaction bulb of concentrated solution and 0 DEG C of stirring and crystallizing sucking filtration, filter cake after 5 hours are cooled under ice bath stirring
Washed and starched with 80ml ice ethanol after draining again with 50ml ice ethanol rinses, HPLC detections are sampled after draining qualified（Middle control 3）Filter cake turns
Move to 20 DEG C～25 DEG C decompression dryings in drip pan and the about 148g of product 1 is obtained after 10 hours；
Filtrate is put to refrigerator and freezes 10 hours and have substantial amounts of faint yellow solid to separate out, filter cake 120ml methanol after sucking filtration
Use 20ml ice methanol drip washing after beating again, HPLC detections are sampled after draining qualified（Middle control 3）Post-drying obtains the about 20g of product 2, filtrate
Carry out with other batches unifying to refine after concentration.
Embodiment three,
Step one, 150g Buddha's warrior attendant alkanones are dissolved in 300ml anhydrous tetrahydro furans, stirring is lower to add 196g bromoethanes, nitrogen
Stir molten clear stand-by to whole under gas shielded.
Step 2, the lithium metal of 17.5g and 60ml anhydrous tetrahydro furans are added to churned mechanically 1000ml reaction bulbs
In, be cooled to while stirring -5 DEG C～0 DEG C start the above-mentioned mixed solution of Deca drip off within about 10 hours, control temperature 10 DEG C～
20℃。
Step 3, drip off after insulation remove cooling system and be warmed to room temperature naturally after 1.5 hours（20 DEG C～25 DEG C）Stir about
10 hours, sampling added water and TLC after reaction is quenched, while after sample presentation GC detections are qualified（Middle control 1）.
Step 4, be cooled to -10 DEG C～-8 DEG C after add phenothiazine 2.5g start the methacrylic chloride control of Deca 104g
Rate of addition processed is by temperature control at -10 DEG C～-5 DEG C.
Step 5, drip off after insulation remove cooling system and be warmed to room temperature naturally after 1 hour（20 DEG C～25 DEG C）Stir about 12
Hour after sample sampling add water be quenched reaction after TLC without raw material point after（Middle control 2）, to Deca in 1000ml reaction bulbs under ice bath
150ml deionized waters are quenched reaction.
Step 6, reactant liquor is transferred to static 45min branch vibration layers after solution is distinguished in 1000ml separatory funnels, is had
Machine layer is transferred to when 20 DEG C of decompression steamings are reserved to no liquid on Rotary Evaporators and removes；
Water layer 80ml petroleum ether extractiones twice, organic layer and will merge and be evaporated, and 250ml oil is added in reactant liquor
Ether dilution after with 300 × 2 10%（Mass ratio）NaOH is washed, and organic layer removes water with after the deionized water wash of 500ml × 3 points again
Layer, organic layer is crossed after being rinsed with 1L petroleum ether after silica gel, and 20 DEG C of mother solution is evaporated to no liquid and reserves；
Then will be equipped with the reaction bulb of concentrated solution and 0 DEG C of stirring and crystallizing sucking filtration, filter cake after 5 hours are cooled under ice bath stirring
Washed and starched with 80ml ice methanol after draining again with 50ml ice ethanol rinses, HPLC detections are sampled after draining qualified（Middle control 3）Filter cake turns
Move to 20 DEG C～25 DEG C decompression dryings in drip pan and the about 151g of product 1 is obtained after 10 hours；
Filtrate is put to refrigerator and freezes 10 hours and have substantial amounts of faint yellow solid to separate out, filter cake 120ml methanol after sucking filtration
Use 20ml ice methanol drip washing after beating again, HPLC detections are sampled after draining qualified（Middle control 3）Post-drying obtains the about 40g of product 2, filtrate
Carry out with other batches unifying to refine after concentration.
Control in reaction：
Claims (3)
1. a kind of preparation method of 2- ethyls -2- adamantanol methacrylates, it is characterised in that comprise the following steps：
Step one, 500g Buddha's warrior attendant alkanones are dissolved in 1550ml anhydrous tetrahydro furans, stirring is lower to add 500g bromoethanes, nitrogen to protect
The lower stirring of shield is to all molten clear stand-by；
Step 2, the anhydrous tetrahydro furan by the lithium metal of 50g and 450ml moisture less than 200ppm, add to churned mechanically
In 5000ml reaction bulbs, -5 DEG C～0 DEG C beginning above-mentioned mixed solution of Deca is cooled to while stirring and is dripped off within about 7 hours, control temperature
Degree is at 10 DEG C～20 DEG C；
Step 3, drip off after insulation 1 hour after remove the room temperature that cooling system rises to 20 DEG C～25 DEG C naturally, stir about 14 is little
When, sampling adds water and TLC after reaction is quenched, while after sample presentation GC detections are qualified；
Step 4, be cooled to -10 DEG C～-8 DEG C after add 5g phenothiazine start Deca 418g methacrylic chloride control Deca
Speed is by temperature control at -10 DEG C～-5 DEG C；
Step 5, drip off after insulation 1 hour after remove the room temperature that cooling system rises to 20 DEG C～25 DEG C naturally, stir about 14 hours
Afterwards sampling add water be quenched reaction after TLC without raw material point after, be quenched to Deca 400ml deionized water in 5000ml reaction bulbs under ice bath
Reaction；
Step 6, reactant liquor is transferred to static 30min branch vibration layer, organic layer after solution is distinguished in 5000ml separatory funnels
It is transferred to when 20 DEG C of decompression steamings are reserved to no liquid on Rotary Evaporators and removes；
Organic layer twice, is merged and is evaporated by water layer 500ml n-hexane extractioies, adds 1500ml normal hexane dilute in reactant liquor
Washed with the NaOH that 800 × 2 mass ratio is 10% after releasing, organic layer removes water with after the deionized water wash of 800ml × 2 points again
Layer, organic layer is crossed after being rinsed with 1.5L normal hexane after silica gel, and 20 DEG C of mother solution is evaporated to no liquid and reserves；
Then will be equipped with the reaction bulb of concentrated solution and 0 DEG C of stirring and crystallizing sucking filtration after 5 hours is cooled under ice bath stirring, filter cake is used
200ml ice methanol is washed and starched after draining again with 100ml ice methanol drip washing, HPLC is sampled after draining and detects qualified, and filter cake is transferred to baking
20 DEG C～25 DEG C decompression dryings obtain product about 510g in disk after 10 hours；
Filtrate is put to refrigerator and freezes 10 hours and have substantial amounts of faint yellow solid to separate out, and filter cake is beaten with 200ml methanol after sucking filtration
Use 50ml ice methanol drip washing again afterwards, HPLC is sampled after draining and detects qualified, post-drying obtains product about 175g, with it after filtrate concentration
Its batch carries out unifying to refine.
2. a kind of preparation method of 2- ethyls -2- adamantanol methacrylates, it is characterised in that comprise the following steps：
Step one, 150g Buddha's warrior attendant alkanones are dissolved in 370ml anhydrous benzene, stirring is lower to add 120g bromoethanes, stirs under nitrogen protection
Mix molten clear stand-by to whole；
Step 2, the magnesium metal of 38.4g and 190ml anhydrous benzene are added to in churned mechanically 1000ml reaction bulbs, side stirring
Drip off within about 5 hours while being cooled to -5 DEG C～0 DEG C and starting the above-mentioned mixed solution of Deca, control temperature is at 10 DEG C～20 DEG C；
Step 3, drip off after insulation 1 hour after remove the room temperature that cooling system rises to 20 DEG C～25 DEG C naturally, stir about 12 is little
When, sampling adds water and TLC after reaction is quenched, while after sample presentation GC detections are qualified；
Step 4, be cooled to -10 DEG C～-8 DEG C after add l, 4- naphthoquinone 4.5g start Deca 166g methacrylic chloride control
Rate of addition is by temperature control at -10 DEG C～-5 DEG C；
Step 5, drip off after insulation 1 hour after remove the room temperature that cooling system rises to 20 DEG C～25 DEG C naturally, stir about 12 hours
Afterwards sampling add water be quenched reaction after TLC without raw material point after, be quenched to Deca 120ml deionized water in 1000ml reaction bulbs under ice bath
Reaction；
Step 6, reactant liquor is transferred to static 30min branch vibration layer, organic layer after solution is distinguished in 1000ml separatory funnels
It is transferred to when 20 DEG C of decompression steamings are reserved to no liquid on Rotary Evaporators and removes；
Water layer is extracted twice with 100ml hexamethylene, and organic layer is merged and is evaporated, and adds 300ml hexamethylene dilute in reactant liquor
Washed with the NaOH that 250 × 2 mass ratio is 10% after releasing, organic layer removes water with after the deionized water wash of 800ml × 2 points again
Layer, organic layer is crossed after being rinsed with 1.5L hexamethylene after silica gel, and 20 DEG C of mother solution is evaporated to no liquid and reserves；
Then will be equipped with the reaction bulb of concentrated solution and 0 DEG C of stirring and crystallizing sucking filtration after 5 hours is cooled under ice bath stirring, filter cake is used
80ml ice ethanol is washed and starched after draining again with 50ml ice ethanol rinses, HPLC is sampled after draining and detects qualified, and filter cake is transferred to drip pan
In 20 DEG C～25 DEG C decompression dryings after 10 hours product about 148g；
Filtrate is put to refrigerator and freezes 10 hours and have substantial amounts of faint yellow solid to separate out, and filter cake is beaten with 120ml methanol after sucking filtration
Use 20ml ice methanol drip washing again afterwards, HPLC is sampled after draining and detects qualified, post-drying obtains product about 20g, with it after filtrate concentration
Its batch carries out unifying to refine.
3. a kind of preparation method of 2- ethyls -2- adamantanol methacrylates, it is characterised in that comprise the following steps：
Step one, 150g Buddha's warrior attendant alkanones are dissolved in 300ml anhydrous tetrahydro furans, stirring is lower to add 196g bromoethanes, nitrogen to protect
The lower stirring of shield is to all molten clear stand-by；
Step 2, the lithium metal of 17.5g and 60ml anhydrous tetrahydro furans are added to in churned mechanically 1000ml reaction bulbs, side
Stirring side is cooled to -5 DEG C～0 DEG C beginning above-mentioned mixed solution of Deca and drips off for about 10 hours, and control temperature is at 10 DEG C～20 DEG C；
Step 3, drip off after insulation 1.5 hours after remove the room temperature that cooling system rises to 20 DEG C～25 DEG C naturally, stir about 10 is little
When, sampling adds water and TLC after reaction is quenched, while after sample presentation GC detections are qualified；
Step 4, be cooled to -10 DEG C～-8 DEG C after add phenothiazine 2.5g start Deca 104g methacrylic chloride control drop
Acceleration is by temperature control at -10 DEG C～-5 DEG C；
Step 5, drip off after insulation 1 hour after remove the room temperature that cooling system rises to 20 DEG C～25 DEG C naturally, stir about 12 hours
Afterwards sampling add water be quenched reaction after TLC without raw material point after, be quenched to Deca 150ml deionized water in 1000ml reaction bulbs under ice bath
Reaction；
Step 6, reactant liquor is transferred to static 45min branch vibration layer, organic layer after solution is distinguished in 1000ml separatory funnels
It is transferred to when 20 DEG C of decompression steamings are reserved to no liquid on Rotary Evaporators and removes；
Organic layer twice, is merged and is evaporated by water layer 80ml petroleum ether extractiones, and the dilution of 250ml petroleum ether is added in reactant liquor
Washed with the NaOH that 300 × 2 mass ratio is 10% afterwards, organic layer uses again branch vibration layer after the deionized water wash of 500ml × 3,
Organic layer is crossed after being rinsed with 1L petroleum ether after silica gel, and 20 DEG C of mother solution is evaporated to no liquid and reserves；
Then will be equipped with the reaction bulb of concentrated solution and 0 DEG C of stirring and crystallizing sucking filtration after 5 hours is cooled under ice bath stirring, filter cake is used
80ml ice methanol is washed and starched after draining again with 50ml ice ethanol rinses, HPLC is sampled after draining and detects qualified, and filter cake is transferred to drip pan
In 20 DEG C～25 DEG C decompression dryings after 10 hours product about 151g；
Filtrate is put to refrigerator and freezes 10 hours and have substantial amounts of faint yellow solid to separate out, and filter cake is beaten with 120ml methanol after sucking filtration
Use 20ml ice methanol drip washing again afterwards, HPLC is sampled after draining and detects qualified, post-drying obtains product about 40g, with it after filtrate concentration
Its batch carries out unifying to refine.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310557438.5A CN104628561B (en) | 2013-11-11 | 2013-11-11 | Preparation method for 2-ethyl-2-adamantanol methacrylate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310557438.5A CN104628561B (en) | 2013-11-11 | 2013-11-11 | Preparation method for 2-ethyl-2-adamantanol methacrylate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104628561A CN104628561A (en) | 2015-05-20 |
| CN104628561B true CN104628561B (en) | 2017-04-12 |
Family
ID=53207858
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310557438.5A Active CN104628561B (en) | 2013-11-11 | 2013-11-11 | Preparation method for 2-ethyl-2-adamantanol methacrylate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104628561B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114085138B (en) * | 2021-11-16 | 2023-12-29 | 徐州博康信息化学品有限公司 | Preparation method of photoresist resin monomer and intermediate thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1429195A (en) * | 2000-05-16 | 2003-07-09 | 株式会社德山 | Process for producing 2-alkyl-2-adamantyl ester |
| JP2004137174A (en) * | 2002-10-16 | 2004-05-13 | Tokuyama Corp | Method for producing 2-alkyl-2-adamantyl (meth)acrylate |
| JP2005002001A (en) * | 2003-06-09 | 2005-01-06 | Chemical Soft R & D Inc | Method for producing high-purity adamantyl compound |
| CN103214349A (en) * | 2012-12-11 | 2013-07-24 | 上海博康精细化工有限公司 | Industrialization production method of 2-substituted-2-adamantanol of photoresist free carbon rigid skeleton structure |
-
2013
- 2013-11-11 CN CN201310557438.5A patent/CN104628561B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1429195A (en) * | 2000-05-16 | 2003-07-09 | 株式会社德山 | Process for producing 2-alkyl-2-adamantyl ester |
| JP2004137174A (en) * | 2002-10-16 | 2004-05-13 | Tokuyama Corp | Method for producing 2-alkyl-2-adamantyl (meth)acrylate |
| JP2005002001A (en) * | 2003-06-09 | 2005-01-06 | Chemical Soft R & D Inc | Method for producing high-purity adamantyl compound |
| CN103214349A (en) * | 2012-12-11 | 2013-07-24 | 上海博康精细化工有限公司 | Industrialization production method of 2-substituted-2-adamantanol of photoresist free carbon rigid skeleton structure |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104628561A (en) | 2015-05-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102060867A (en) | Method for preparing potassium trifluoroborate series compounds | |
| CN102127092A (en) | Preparation of Everolimus | |
| CN104910012B (en) | A kind of method preparing 1-ethylcyclohexyl acrylate | |
| CN104628557B (en) | The preparation method of 2-methyl-2-adamantanol acrylate | |
| CN102206151B (en) | Synthetic method of royaljelly acid | |
| CN104628561B (en) | Preparation method for 2-ethyl-2-adamantanol methacrylate | |
| CN104513161B (en) | A kind of pentaerythritol acrylate preparation method of mixture | |
| CN109879755A (en) | The preparation method of 1- ethylcyclohexyl (methyl) acrylate | |
| JP2005314383A (en) | Adamantane derivative and its preparation method | |
| CN104628562A (en) | Preparation method for 2-ethyl-2-adamantanol acrylate | |
| CN101792389A (en) | Method for producing adamantyl (meth)acrylates | |
| CN113979454B (en) | Preparation method of alkali metal fluorosulfonate | |
| JP6478447B2 (en) | Method for producing adamantyl (meth) acrylate compound | |
| CN104230712A (en) | Method for preparing 2-isopropyl-2-adamantyl acrylate | |
| JP6503227B2 (en) | Purification method of 4-hydroxybenzoic acid long chain ester | |
| CN108299192A (en) | A kind of metal salt compound crystal form and preparation method thereof of tafluprost acid | |
| CN104418731A (en) | Preparation method of adamantine diester | |
| CN104628526B (en) | A kind of preparation method of adamantane triol | |
| CN106905358B (en) | Preparation of vitamin D3Process for preparing analogue intermediates | |
| CN102351653B (en) | Method for purifying 2, 4-di-(1-phenylisopropyl) phenol with secondary recrystallization | |
| CN107200770B (en) | In the synthesis of special plast ketone eposide isomers efficiently separate and circulation utilization method | |
| CN106631911A (en) | Method for synthesizing cis-tritosylate | |
| CN106316851B (en) | A kind of new method of methyl chloroacetate purification | |
| CN101177398A (en) | Method for refining trifluoro willow | |
| CN103910668B (en) | A kind of preparation method of 3 alkyl-indol |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| EXSB | Decision made by sipo to initiate substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| ASS | Succession or assignment of patent right |
Owner name: SHANGHAI B + C PHARMACEUTICAL R + D CO., LTD. Free format text: FORMER OWNER: FU ZHIWEI Effective date: 20150806 Owner name: XUZHOU B + C INFORMATIONAL CHEMICAL PRODUCTS CO., Effective date: 20150806 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20150806 Address after: 200233 Shanghai Road, Guiping, building 702, room 4, building 333, room Applicant after: Shanghai B & C Pharmaceutical R & D Co., Ltd. Applicant after: B&C (Xuzhou) Chemical Co., Ltd. Address before: North Sau village Gulou District of Nanjing city in Jiangsu province 210008 No. 22 unit 401 room Applicant before: Fu Zhiwei |
|
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20201113 Address after: 221300 chemical agglomeration area, Pizhou Economic Development Zone, Jiangsu, Xuzhou Patentee after: XUZHOU B&C CHEMICAL Co.,Ltd. Address before: 200233, room 4, building 333, 702 Guiping Road, Shanghai, Xuhui District Patentee before: SHANGHAI B&C CHEMICAL Co.,Ltd. Patentee before: XUZHOU B&C CHEMICAL Co.,Ltd. |
|
| TR01 | Transfer of patent right |