CN104628561A - Preparation method for 2-ethyl-2-adamantanol methacrylate - Google Patents
Preparation method for 2-ethyl-2-adamantanol methacrylate Download PDFInfo
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- CN104628561A CN104628561A CN201310557438.5A CN201310557438A CN104628561A CN 104628561 A CN104628561 A CN 104628561A CN 201310557438 A CN201310557438 A CN 201310557438A CN 104628561 A CN104628561 A CN 104628561A
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- adamantanol
- methacrylic ester
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- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- DCTVCFJTKSQXED-UHFFFAOYSA-N (2-ethyl-2-adamantyl) 2-methylprop-2-enoate Chemical compound C1C(C2)CC3CC1C(CC)(OC(=O)C(C)=C)C2C3 DCTVCFJTKSQXED-UHFFFAOYSA-N 0.000 title abstract 3
- 238000006243 chemical reaction Methods 0.000 claims abstract description 59
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 44
- 238000000034 method Methods 0.000 claims abstract description 15
- RDHPKYGYEGBMSE-UHFFFAOYSA-N bromoethane Chemical compound CCBr RDHPKYGYEGBMSE-UHFFFAOYSA-N 0.000 claims abstract description 12
- VHRYZQNGTZXDNX-UHFFFAOYSA-N methacryloyl chloride Chemical compound CC(=C)C(Cl)=O VHRYZQNGTZXDNX-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000002904 solvent Substances 0.000 claims abstract description 12
- 229910052751 metal Inorganic materials 0.000 claims abstract description 8
- 239000002184 metal Substances 0.000 claims abstract description 8
- 239000003112 inhibitor Substances 0.000 claims abstract description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 21
- -1 diamantane ketone Chemical class 0.000 claims description 21
- 239000007788 liquid Substances 0.000 claims description 20
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 claims description 17
- YUBKBLFRGDNIDR-UHFFFAOYSA-N 2-ethyladamantan-2-ol Chemical compound C1C(C2)CC3CC1C(CC)(O)C2C3 YUBKBLFRGDNIDR-UHFFFAOYSA-N 0.000 claims description 17
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 14
- 238000000605 extraction Methods 0.000 claims description 11
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 229910052744 lithium Inorganic materials 0.000 claims description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 7
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 5
- 238000002425 crystallisation Methods 0.000 claims description 4
- 230000008025 crystallization Effects 0.000 claims description 4
- 239000004215 Carbon black (E152) Substances 0.000 claims description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 229930195733 hydrocarbon Natural products 0.000 claims description 3
- 150000002430 hydrocarbons Chemical class 0.000 claims description 3
- 150000001805 chlorine compounds Chemical class 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 150000002170 ethers Chemical class 0.000 claims description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 2
- 150000004053 quinones Chemical class 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 abstract description 5
- 238000009776 industrial production Methods 0.000 abstract description 3
- 238000006116 polymerization reaction Methods 0.000 abstract description 2
- 238000000746 purification Methods 0.000 abstract description 2
- IYKFYARMMIESOX-SPJNRGJMSA-N adamantanone Chemical compound C([C@H](C1)C2)[C@H]3C[C@@H]1C(=O)[C@@H]2C3 IYKFYARMMIESOX-SPJNRGJMSA-N 0.000 abstract 1
- 238000010791 quenching Methods 0.000 abstract 1
- 230000000171 quenching effect Effects 0.000 abstract 1
- 239000000376 reactant Substances 0.000 abstract 1
- 238000001308 synthesis method Methods 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 30
- 239000000047 product Substances 0.000 description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 16
- 239000000243 solution Substances 0.000 description 16
- 238000003756 stirring Methods 0.000 description 16
- 239000012044 organic layer Substances 0.000 description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 13
- 238000005070 sampling Methods 0.000 description 12
- 239000010410 layer Substances 0.000 description 10
- 238000001816 cooling Methods 0.000 description 9
- 239000012065 filter cake Substances 0.000 description 9
- 239000007789 gas Substances 0.000 description 9
- 238000005406 washing Methods 0.000 description 9
- 238000009413 insulation Methods 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 230000006837 decompression Effects 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 239000000706 filtrate Substances 0.000 description 6
- 238000004128 high performance liquid chromatography Methods 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 238000000967 suction filtration Methods 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 238000010790 dilution Methods 0.000 description 5
- 239000012895 dilution Substances 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 239000000741 silica gel Substances 0.000 description 5
- 229910002027 silica gel Inorganic materials 0.000 description 5
- 150000001336 alkenes Chemical class 0.000 description 4
- 238000010009 beating Methods 0.000 description 4
- 239000012452 mother liquor Substances 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- 238000001953 recrystallisation Methods 0.000 description 4
- 230000003068 static effect Effects 0.000 description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 3
- 206010013786 Dry skin Diseases 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000012141 concentrate Substances 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- ZICQBHNGXDOVJF-UHFFFAOYSA-N diamantane Chemical compound C1C2C3CC(C4)CC2C2C4C3CC1C2 ZICQBHNGXDOVJF-UHFFFAOYSA-N 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 238000007710 freezing Methods 0.000 description 3
- 230000008014 freezing Effects 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000009955 starching Methods 0.000 description 3
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- FRASJONUBLZVQX-UHFFFAOYSA-N 1,4-naphthoquinone Chemical class C1=CC=C2C(=O)C=CC(=O)C2=C1 FRASJONUBLZVQX-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001312 dry etching Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000013307 optical fiber Substances 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000012958 reprocessing Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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 provide a kind of preparation method of 2-ethyl-2-adamantanol methacrylic ester.
Background technology
Diamantane is a kind of straight, symmetrical, high stability caged hydrocarbon, because have the structure that four cyclohexane rings are condensed into cage type, so, be the compound that a kind of symmetry is high and stable.Its derivative known relates to the fields such as medicine, aerospace, functional materials, refining of petroleum.
It is worth mentioning that, because diamantane has the such as character such as optical characteristics, thermotolerance, therefore, its derivative is often used in optic disc base board, optical fiber or lens lamp.Can be used as semi-conductor photo-resist, photosemiconductor sealing agent, optoelectronic component (photoconductive tube, optical communication lens and optical thin film etc.) and their caking agent.
Wherein, the electronic component manufactured using alkyl adamantane esters of acrylic acid as raw material, the dry etching patience in semiconductor fabrication process is high, and the development prospect as semi-conductor material is wide.
The alkyl diamantane ester adopting currently known methods of the prior art to obtain is often because side reaction too much produces a large amount of impurity, cause sepn process complicated, pure products cannot be obtained by modes such as crystallizations, and then cause productive rate on the low side, cost is difficult to control, and also directly causes it to be not easily applied to industrial production.
Summary of the invention
The present invention is intended to overcome above-mentioned defect, provides a kind of high yield, high purity, environmental protection, cheap, the preparation method that can carry out industrial 2-ethyl-2-adamantanol methacrylic ester.
For achieving the above object, the preparation method of the 2-ethyl-2-adamantanol methacrylic ester that the present invention relates to, is characterized in that, comprise the following steps:
Step one, monobromethane is dripped in the diamantane ketone being dissolved in solvent, form preparation liquid one;
In the present invention, generally selecting and diamantane ketone is dissolved in solvent, adding monobromethane when stirring, be stirred to whole molten stand-by clearly under the protection of protection gas.
In the present invention, above-mentioned solvent can be selected from the mixture of one or more in anhydrous tetrahydro furan, Anaesthetie Ether, toluene, benzene, alkane, dry-out benzene.
Protection gas can be selected from the rare gas elementes such as nitrogen, argon gas, helium.
In addition, the mol ratio of diamantane ketone and monobromethane is 1:1.1-1.8.Be preferably 1:1.4-1.8.
It is 20-50% that diamantane is dissolved in the mass percent concentration after solvent, is preferably 30-40%.React too violent when the concentration is too high; Solute too disperses when the concentration is too low, causes reaction not exclusively.
Step 2, the solvent be placed in by metal, form preparation liquid two.
In the present invention, the mol ratio of diamantane ketone and metallic lithium is 1:1.6-2.5.Be preferably 1:2.1-2.5.
Metal can be the metal such as metallic lithium, MAGNESIUM METAL.
The mass percent concentration that metal accounts for solution is 1-30%, selects 10-20%.The concentration of metal is unsuitable too high, otherwise reaction can be caused too violent, and produces a large amount of heat, thus destroys the stability of reaction.
Solvent can be selected from the mixture of one or more in anhydrous tetrahydro furan, Anaesthetie Ether, toluene, benzene, alkane, dry-out benzene.
In addition, for ensureing the high efficiency of reaction, preparing in lithium reagent process and will strictly control moisture and air, so this step also preferably selects protection gas shielded.
Step 3, preparation liquid one slowly to be dropped in preparation liquid two.
It should be noted that this step preferably selects protection gas shielded.
In the present invention, this step should the temperature below 0 DEG C start to drip, and in the process of dropping, temperature preferably controls between 10 DEG C-20 DEG C, and the speed of dropping preferably controls at 0.1-1%/min, dropwises in about 5-10 hour.
Be added dropwise to complete rear insulation 0.5-2 hour.
Step 4, naturally rise to room temperature after, reaction 10-20 hour, the preferred reaction time is 10-14 hour.
The judgement of above-mentioned reaction end preferably adopts, get sample add water cancellation reaction after, the pattern that TLC detects in conjunction with GC.
Step 5, be cooled to less than 0 DEG C, be preferably cooled to less than-5 DEG C, add poly-resist.
Poly-resist can be selected from the composition of one or more in phenolic inhibitor, quinones stopper, arene nitro compound stopper.
The quality of poly-resist is the 0.1-10% of the quality of diamantane ketone, is preferably 0.5-1.5%.
Step 6, dropping methacrylic chloride;
The mol ratio of diamantane ketone and methacrylic chloride is 1:1.0-1.6.Be preferably 1:1.2-1.6.
It should be noted that the speed dripping methacrylic chloride to be controlled by system temperature to be advisable between-10 DEG C ~-5 DEG C, should be added dropwise to complete rear insulation 0.5-1.5 hour and be advisable.
Step 7, naturally rise to room temperature after, reaction 10-20 hour, the preferred reaction time is 10-14 hour.
The judgement of above-mentioned reaction end preferably adopts, and gets sample and adds water after cancellation reaction, whether there is raw material be as the criterion with TLC examination.
Step 8, reaction terminate after add water cancellation reaction.
The usage quantity of water is 0.1-5 times of diamantane ketone quality.
In addition, this cancellation process that adds water should be carried out in ice bath, and the speed dripping water should to control the temperature of reaction system to be advisable within 20 DEG C.
Step 9, obtain 2-ethyl-2-adamantanol methacrylic ester through aftertreatment.
Aftertreatment in above-mentioned steps is extraction at least one times, crystallization at least one times and at least one times concentrated.
Concrete step is: after (1) static layering, gets organic layer and carries out underpressure distillation.
(2) water layer is with after extraction liquid extraction at least one times, merges organic layer and carries out underpressure distillation.
(3) with after extraction liquid dilution, repeatedly washing is neutralized with the alkali lye after dilution.
(4) after repeatedly washing, organic layer is got, by concentrated after filtered through silica gel.
(5) after ice bath crystallization extremely goes out crystalline substance completely, filtration, alcohol wash.
(6) productive rate repeatedly obtaining sterling after recrystallization is 65-99%.
It is worthy of note, can not by complete for solvent evaporate to dryness during refinement mother liquor secondary recovery, steam to micro-dry time add reprocessing after alcohol making beating, pull an oar with alcohol again as defective.
Wherein, one or more being selected from alkane, ethers, naphthenic hydrocarbon, ester class of extraction liquid obtain mixture.
The consumption of silica gel is 0.1-10 times of diamantane ketone quality.
The quality of extraction liquid is 1-50 times of diamantane ketone, is preferably 4-10 doubly.
The optional mass concentration of alkali lye of neutralization is the sodium hydroxide, potassium hydroxide, sodium bicarbonate etc. of 5-15%.
Alcohol wash process selects alcohol to be selected from methyl alcohol, ethanol etc., and quality is 0.1-5 times of diamantane ketone.
In addition, because product involved in the present invention is very responsive to heat, temperature time underpressure distillation (concentrating) should not exceed 20 DEG C, otherwise has impurity (as: alkene) generation.
Concrete reaction equation is as follows:
In addition, can be replaced with any halogenated compound at monobromethane of the present invention, methacrylic chloride can be replaced with the chloride compounds replaced arbitrarily, for the preparation of the derivative of 2-diamantane ester.
the effect of invention and effect
The present invention obtains by the control of the conditions such as protection gas shielded, low-temp reaction, reaction times a kind of method preparing 2-ethyl-2-adamantanol methacrylic ester that by product is few, sepn process is simple, product purity is high, productive rate is high.
Empirical tests finds, product prepared by the present invention is very responsive to heat, so require to want strict temperature control when reacting.For ensureing product purity, improve product yield, the present invention carries out under advocating temperature of reaction, thickening temperature to be controlled the cold condition below 20 DEG C, thus avoids the generation of impurity (alkene).In addition, impurity alkene, once be created on recrystallization, also can cause a large amount of product loss, and therefore the temperature of re-crystallization stage also should control below 20 DEG C.In addition, during oven dry, temperature is no more than 25 DEG C, otherwise there will be molten state thus occur polymerization affect quality product and yield.
Consider the said products characteristic, for ensureing conversion rate of products, reduce production cost further, cancellation step of reaction after completion of the reaction, the speed dripping water will be no more than 20 DEG C with reacting liquid temperature and be advisable, otherwise may have the generation of impurity alkene.
The present invention also points out, prepares in lithium reagent process and will strictly control moisture and air, so will adopt the measure of protection gas shielded.
Unaffected for ensureing product yield, the present invention also limits the process of recrystallization.
The present invention also points out, because product requires higher to metal ion, so, except protecting except gas shielded, also preferably select deionized water in post-processing stages.
In sum, in synthetic method provided by the invention, by the selection of each step reaction condition, as: temperature of reaction, reaction ratio, reaction times, reaction raw materials etc., overcome prior art open in, purification difficult, high cost, reaction yield are low, product purity is low, be not suitable for the problems such as large-scale industrial production.
Embodiment
Embodiment one,
Step one, be dissolved in 1550ml anhydrous tetrahydro furan by 500g diamantane ketone, add 500g monobromethane under stirring, stirred under nitrogen atmosphere is to whole molten stand-by clearly.
Step 2, the metallic lithium of 50g and 450ml anhydrous tetrahydro furan (moisture is less than 200ppm) added in the churned mechanically 5000ml reaction flask of band, be cooled to-5 DEG C ~ 0 DEG C while stirring to start to drip above-mentioned mixing solutions and drip off for about 7 hours, control temperature is at 10 DEG C ~ 20 DEG C.
Step 3, drip off rear insulation and remove cooling system after 1 hour and naturally rise to room temperature (20 DEG C ~ 25 DEG C) stir about 14 hours, sampling adds water TLC after cancellation reaction, simultaneously sample presentation GC detect qualified after (middle control 1).
Step 4, be cooled to-10 DEG C ~-8 DEG C after add 5g thiodiphenylamine and start to drip 418g methacrylic chloride and control rate of addition temperature is controlled at-10 DEG C ~-5 DEG C.
Step 5, drip off rear insulation remove after 1 hour cooling system naturally rise to room temperature (20 DEG C ~ 25 DEG C) stir about after 14 hours sampling add water cancellation reaction after TLC without (middle control 2) after raw material point, drip in 5000ml reaction flask under ice bath the cancellation of 400ml deionized water reaction.
Step 6, reaction solution is transferred to static 30min branch vibration layer after solution is distinguished in 5000ml separating funnel, organic layer is transferred to 20 DEG C of decompressions on Rotary Evaporators and steams and take off when absence of liquid reserves;
Water layer 500ml n-hexane extraction twice, by organic layer and merging also evaporate to dryness, add in reaction solution 1500ml normal hexane dilution after with 800 × 2 10%(mass ratio) NaOH wash, organic layer uses branch vibration layer after the deionized water wash of 800ml × 2 again, after rinsing with 1.5L normal hexane after organic layer crosses silica gel, 20 DEG C, mother liquor is evaporated to absence of liquid and reserves;
Then the reaction flask that concentrated solution is housed is stirred borehole cooling to 0 DEG C stirring and crystallizing suction filtration after 5 hours at ice bath, filter cake 200ml ice methyl alcohol uses the drip washing of 100ml ice methyl alcohol after washing and starching and draining again, drain rear sampling HPLC detect qualified (middle control 3) filter cake to be transferred in drip pan 20 DEG C ~ 25 DEG C decompression dryings after 10 hours product 1 about 510g;
Filtrate is put to refrigerator has again a large amount of faint yellow solid to separate out for freezing 10 hours, the drip washing of 50ml ice methyl alcohol is used again after the making beating of filter cake 200ml methyl alcohol after suction filtration, drain rear sampling HPLC detection qualified (middle control 3) post-drying and obtain product 2 about 175g, filtrate concentrates afterwards and other batch carries out unifying to refine.
Embodiment two,
Step one, be dissolved in 370ml dry-out benzene by 150g diamantane ketone, add 120g monobromethane under stirring, stirred under nitrogen atmosphere is to whole molten stand-by clearly.
Step 2, the MAGNESIUM METAL of 38.4g and 190ml dry-out benzene to be added in the churned mechanically 1000ml reaction flask of band, be cooled to-5 DEG C ~ 0 DEG C while stirring and start to drip above-mentioned mixing solutions and drip off for about 5 hours, control temperature is at 10 DEG C ~ 20 DEG C.
Step 3, drip off rear insulation and remove cooling system after 1 hour and naturally rise to room temperature (20 DEG C ~ 25 DEG C) stir about 12 hours, sampling adds water TLC after cancellation reaction, simultaneously sample presentation GC detect qualified after (middle control 1).
Step 4, be cooled to-10 DEG C ~-8 DEG C after add l, 4-naphthoquinones 4.5g starts to drip 166g methacrylic chloride and controls rate of addition and control temperature at-10 DEG C ~-5 DEG C.
Step 5, drip off rear insulation remove after 1 hour cooling system naturally rise to room temperature (20 DEG C ~ 25 DEG C) stir about after 12 hours sampling add water cancellation reaction after TLC without (middle control 2) after raw material point, drip in 1000ml reaction flask under ice bath the cancellation of 120ml deionized water reaction.
Step 6, reaction solution is transferred to static 30min branch vibration layer after solution is distinguished in 1000ml separating funnel, organic layer is transferred to 20 DEG C of decompressions on Rotary Evaporators and steams and take off when absence of liquid reserves;
Water layer 100ml hexanaphthene extracting twice, by organic layer and merging also evaporate to dryness, add in reaction solution 300ml hexanaphthene dilution after with 250 × 2 10%(mass ratio) NaOH wash, organic layer uses branch vibration layer after the deionized water wash of 800ml × 2 again, after rinsing with 1.5L hexanaphthene after organic layer crosses silica gel, 20 DEG C, mother liquor is evaporated to absence of liquid and reserves;
Then the reaction flask that concentrated solution is housed is stirred borehole cooling to 0 DEG C stirring and crystallizing suction filtration after 5 hours at ice bath, filter cake 80ml ice ethanol uses 50ml ice ethanol rinse after washing and starching and draining again, drain rear sampling HPLC detect qualified (middle control 3) filter cake to be transferred in drip pan 20 DEG C ~ 25 DEG C decompression dryings after 10 hours product 1 about 148g;
Filtrate is put to refrigerator has again a large amount of faint yellow solid to separate out for freezing 10 hours, the drip washing of 20ml ice methyl alcohol is used again after the making beating of filter cake 120ml methyl alcohol after suction filtration, drain rear sampling HPLC detection qualified (middle control 3) post-drying and obtain product 2 about 20g, filtrate concentrates afterwards and other batch carries out unifying to refine.
Embodiment three,
Step one, be dissolved in 300ml anhydrous tetrahydro furan by 150g diamantane ketone, add 196g monobromethane under stirring, stirred under nitrogen atmosphere is to whole molten stand-by clearly.
Step 2, the metallic lithium of 17.5g and 60ml anhydrous tetrahydro furan to be added in the churned mechanically 1000ml reaction flask of band, be cooled to-5 DEG C ~ 0 DEG C while stirring and start to drip above-mentioned mixing solutions and drip off for about 10 hours, control temperature is at 10 DEG C ~ 20 DEG C.
Step 3, drip off rear insulation and remove cooling system after 1.5 hours and naturally rise to room temperature (20 DEG C ~ 25 DEG C) stir about 10 hours, sampling adds water TLC after cancellation reaction, simultaneously sample presentation GC detect qualified after (middle control 1).
Step 4, be cooled to-10 DEG C ~-8 DEG C after add thiodiphenylamine 2.5g and start to drip 104g methacrylic chloride and control rate of addition temperature is controlled at-10 DEG C ~-5 DEG C.
Step 5, drip off rear insulation remove after 1 hour cooling system naturally rise to room temperature (20 DEG C ~ 25 DEG C) stir about after 12 hours sampling add water cancellation reaction after TLC without (middle control 2) after raw material point, drip in 1000ml reaction flask under ice bath the cancellation of 150ml deionized water reaction.
Step 6, reaction solution is transferred to static 45min branch vibration layer after solution is distinguished in 1000ml separating funnel, organic layer is transferred to 20 DEG C of decompressions on Rotary Evaporators and steams and take off when absence of liquid reserves;
Water layer 80ml petroleum ether extraction twice, by organic layer and merging also evaporate to dryness, add in reaction solution 250ml sherwood oil dilution after with 300 × 2 10%(mass ratio) NaOH wash, organic layer uses branch vibration layer after the deionized water wash of 500ml × 3 again, after rinsing with 1L sherwood oil after organic layer crosses silica gel, 20 DEG C, mother liquor is evaporated to absence of liquid and reserves;
Then the reaction flask that concentrated solution is housed is stirred borehole cooling to 0 DEG C stirring and crystallizing suction filtration after 5 hours at ice bath, filter cake 80ml ice methyl alcohol uses 50ml ice ethanol rinse after washing and starching and draining again, drain rear sampling HPLC detect qualified (middle control 3) filter cake to be transferred in drip pan 20 DEG C ~ 25 DEG C decompression dryings after 10 hours product 1 about 151g;
Filtrate is put to refrigerator has again a large amount of faint yellow solid to separate out for freezing 10 hours, the drip washing of 20ml ice methyl alcohol is used again after the making beating of filter cake 120ml methyl alcohol after suction filtration, drain rear sampling HPLC detection qualified (middle control 3) post-drying and obtain product 2 about 40g, filtrate concentrates afterwards and other batch carries out unifying to refine.
Control in reaction:
Claims (10)
1. a preparation method for 2-ethyl-2-adamantanol methacrylic ester, is characterized in that, comprise the following steps:
Step one, monobromethane is dripped in the diamantane ketone being dissolved in solvent, form preparation liquid one;
Step 2, the solvent be placed in by metal, form preparation liquid two;
Step 3, preparation liquid one is slowly dropped in preparation liquid two;
Step 4, naturally rise to room temperature after, reaction 10-20 hour;
Under step 5, system temperature below 0 DEG C, add poly-resist, drip methacrylic chloride;
Step 6, naturally rise to room temperature after, reaction 10-20 hour;
Step 7, the cancellation that adds water reaction;
Step 8, obtain 2-ethyl-2-adamantanol methacrylic ester through aftertreatment;
Wherein, in the dropping process of described step 3, temperature remains on less than 20 DEG C;
In the dropping process of described step 5, temperature remains on less than 0 DEG C;
The cancellation process that adds water of described step 7 is carried out in ice bath;
Described metal is metallic lithium or MAGNESIUM METAL.
2. the preparation method of a kind of 2-ethyl-2-adamantanol methacrylic ester as claimed in claim 1, is characterized in that: the mol ratio of described diamantane ketone, metallic lithium, monobromethane, methacrylic chloride is 1:1.6-2.5:1.1-1.8:1.0-1.6.
3. the preparation method of a kind of 2-ethyl-2-adamantanol methacrylic ester as claimed in claim 1, is characterized in that: the mol ratio of described diamantane ketone, metallic lithium, monobromethane, methacrylic chloride is preferably 1:2.1-2.5:1.4-1.8:1.2-1.6.
4. the preparation method of a kind of 2-ethyl-2-adamantanol methacrylic ester as claimed in claim 1, is characterized in that: described step 3 is preferably carried out under the protection of protection gas.
5. the preparation method of a kind of 2-ethyl-2-adamantanol methacrylic ester as claimed in claim 1, is characterized in that: described solvent can be selected from the mixture of one or more in anhydrous tetrahydro furan, Anaesthetie Ether, toluene, benzene, alkane.
6. the preparation method of a kind of 2-ethyl-2-adamantanol methacrylic ester as claimed in claim 1, is characterized in that: described poly-resist can be selected from the composition of one or more in phenolic inhibitor, quinones stopper, arene nitro compound stopper.
7. the preparation method of a kind of 2-ethyl-2-adamantanol methacrylic ester as claimed in claim 1, is characterized in that: the aftertreatment in described step 8 is extraction at least one times, crystallization at least one times and at least one times concentrated.
8. the preparation method of a kind of 2-ethyl-2-adamantanol methacrylic ester as claimed in claim 6, is characterized in that: one or more being selected from alkane, ethers, naphthenic hydrocarbon, ester class of extraction liquid of described extraction obtain mixture.
9. the preparation method of a kind of 2-ethyl-2-adamantanol methacrylic ester as claimed in claim 6, is characterized in that: described concentrated time temperature lower than 20 DEG C.
10. the preparation method of a kind of 2-ethyl-2-adamantanol methacrylic ester as described in as arbitrary in claim 1 to 9, it is characterized in that: described monobromethane can be replaced with any halogenated compound, described methacrylic chloride can be replaced with the chloride compounds replaced arbitrarily, for the preparation of the derivative of 2-diamantane ester.
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| 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 |
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| 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 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114085138A (en) * | 2021-11-16 | 2022-02-25 | 徐州博康信息化学品有限公司 | Preparation method of photoresist resin monomer and intermediate thereof |
| 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 |
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