CN112812010A - Method for synthesizing adamantane ester (methyl) acrylate - Google Patents
Method for synthesizing adamantane ester (methyl) acrylate Download PDFInfo
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- ORILYTVJVMAKLC-UHFFFAOYSA-N adamantane Chemical compound C1C(C2)CC3CC1CC2C3 ORILYTVJVMAKLC-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 238000000034 method Methods 0.000 title claims abstract description 18
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 14
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 title description 2
- 150000002148 esters Chemical class 0.000 title description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 21
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 19
- IYKFYARMMIESOX-UHFFFAOYSA-N adamantanone Chemical compound C1C(C2)CC3CC1C(=O)C2C3 IYKFYARMMIESOX-UHFFFAOYSA-N 0.000 claims abstract description 17
- CERQOIWHTDAKMF-UHFFFAOYSA-N alpha-methacrylic acid Natural products CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract description 15
- 150000001335 aliphatic alkanes Chemical class 0.000 claims abstract description 9
- 150000008064 anhydrides Chemical class 0.000 claims abstract description 6
- 125000004390 alkyl sulfonyl group Chemical group 0.000 claims abstract description 5
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 4
- 239000007818 Grignard reagent Substances 0.000 claims abstract description 3
- 150000004795 grignard reagents Chemical class 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 35
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 24
- 238000001816 cooling Methods 0.000 claims description 23
- 238000001914 filtration Methods 0.000 claims description 14
- 239000007787 solid Substances 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 13
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 12
- 239000012295 chemical reaction liquid Substances 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 10
- 239000003112 inhibitor Substances 0.000 claims description 8
- 238000006116 polymerization reaction Methods 0.000 claims description 8
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 claims description 6
- 150000007530 organic bases Chemical class 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000011777 magnesium Substances 0.000 claims description 5
- 229910052749 magnesium Inorganic materials 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- 150000008052 alkyl sulfonates Chemical class 0.000 claims description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052794 bromium Inorganic materials 0.000 claims description 4
- 239000000460 chlorine Substances 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 150000002367 halogens Chemical class 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 2
- 150000001924 cycloalkanes Chemical class 0.000 claims description 2
- 229940043279 diisopropylamine Drugs 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 2
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- -1 adamantane ester Chemical class 0.000 abstract description 9
- 238000001308 synthesis method Methods 0.000 abstract description 6
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 32
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 239000012074 organic phase Substances 0.000 description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 11
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 9
- 229950000688 phenothiazine Drugs 0.000 description 9
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 8
- 239000012043 crude product Substances 0.000 description 8
- 238000001035 drying Methods 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 239000000741 silica gel Substances 0.000 description 8
- 229910002027 silica gel Inorganic materials 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000008346 aqueous phase Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- OSQPUMRCKZAIOZ-UHFFFAOYSA-N carbon dioxide;ethanol Chemical compound CCO.O=C=O OSQPUMRCKZAIOZ-UHFFFAOYSA-N 0.000 description 5
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 5
- YYROPELSRYBVMQ-UHFFFAOYSA-N 4-toluenesulfonyl chloride Chemical compound CC1=CC=C(S(Cl)(=O)=O)C=C1 YYROPELSRYBVMQ-UHFFFAOYSA-N 0.000 description 4
- 239000012044 organic layer Substances 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 238000004042 decolorization Methods 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 230000001502 supplementing effect Effects 0.000 description 3
- NLNVUFXLNHSIQH-UHFFFAOYSA-N (2-ethyl-2-adamantyl) prop-2-enoate Chemical compound C1C(C2)CC3CC1C(CC)(OC(=O)C=C)C2C3 NLNVUFXLNHSIQH-UHFFFAOYSA-N 0.000 description 2
- FDYDISGSYGFRJM-UHFFFAOYSA-N (2-methyl-2-adamantyl) 2-methylprop-2-enoate Chemical compound C1C(C2)CC3CC1C(OC(=O)C(=C)C)(C)C2C3 FDYDISGSYGFRJM-UHFFFAOYSA-N 0.000 description 2
- VULULCJGEQPEOV-UHFFFAOYSA-N (2-propan-2-yl-2-adamantyl) prop-2-enoate Chemical compound C1C(C2)CC3CC1C(C(C)C)(OC(=O)C=C)C2C3 VULULCJGEQPEOV-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 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 description 2
- RJUIDDKTATZJFE-UHFFFAOYSA-N but-2-enoyl chloride Chemical compound CC=CC(Cl)=O RJUIDDKTATZJFE-UHFFFAOYSA-N 0.000 description 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- DCUFMVPCXCSVNP-UHFFFAOYSA-N methacrylic anhydride Chemical compound CC(=C)C(=O)OC(=O)C(C)=C DCUFMVPCXCSVNP-UHFFFAOYSA-N 0.000 description 2
- 229920002120 photoresistant polymer Polymers 0.000 description 2
- NAMYKGVDVNBCFQ-UHFFFAOYSA-N 2-bromopropane Chemical compound CC(C)Br NAMYKGVDVNBCFQ-UHFFFAOYSA-N 0.000 description 1
- UZFMOKQJFYMBGY-UHFFFAOYSA-N 4-hydroxy-TEMPO Chemical compound CC1(C)CC(O)CC(C)(C)N1[O] UZFMOKQJFYMBGY-UHFFFAOYSA-N 0.000 description 1
- XESZUVZBAMCAEJ-UHFFFAOYSA-N 4-tert-butylcatechol Chemical compound CC(C)(C)C1=CC=C(O)C(O)=C1 XESZUVZBAMCAEJ-UHFFFAOYSA-N 0.000 description 1
- 238000003747 Grignard reaction Methods 0.000 description 1
- 239000012359 Methanesulfonyl chloride Substances 0.000 description 1
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229960003750 ethyl chloride Drugs 0.000 description 1
- 238000011081 inoculation Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- QARBMVPHQWIHKH-UHFFFAOYSA-N methanesulfonyl chloride Chemical compound CS(Cl)(=O)=O QARBMVPHQWIHKH-UHFFFAOYSA-N 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- ARJOQCYCJMAIFR-UHFFFAOYSA-N prop-2-enoyl prop-2-enoate Chemical compound C=CC(=O)OC(=O)C=C ARJOQCYCJMAIFR-UHFFFAOYSA-N 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/03—Preparation of carboxylic acid esters by reacting an ester group with a hydroxy group
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for synthesizing adamantane ester (meth) acrylate, which relates to the field of organic synthesis, and comprises the following steps: reacting (methyl) acrylic acid with alkyl sulfonyl chloride to generate mixed anhydride S1; the second step is that: under the action of a lithium reagent or a Grignard reagent, 2-adamantanone reacts with halogenated alkane to generate an intermediate S2; the third step: the mixed anhydride S1 and the intermediate S2 react to form adamantane (meth) acrylate. The invention provides a method for synthesizing adamantane ester (meth) acrylate, which provides more selectivity for synthesizing the adamantane ester (meth) acrylate. The synthesis method has the advantages of high yield, high product purity and low synthesis cost.
Description
Technical Field
The invention relates to the field of organic synthesis, in particular to a method for synthesizing adamantane ester (meth) acrylate.
Background
Photoresist is one of the key materials for fine pattern processing in microelectronics technologies. Mainly comprises polymeric resin, a photoacid generator and other auxiliary agents.
Adamantane (meth) acrylate is a resin monomer widely used for 193nm photoresist, and at present, the main synthesis method is to use adamantanone as a raw material, convert the adamantanone into 1-alkyl adamantanol through a lithium reagent or a Grignard reaction, and then carry out an esterification reaction with (meth) acryloyl chloride or (meth) acrylic anhydride to obtain the adamantane (meth) acrylate. Relatively few reports have been made of the transesterification of 1-alkyladamantols with (meth) acrylates to give adamantane (meth) acrylates.
In the prior art, the esterification reaction is mostly carried out by adopting (methyl) acrylic anhydride or (methyl) acryloyl chloride, the synthetic route is single, and the prices of the (methyl) acrylic anhydride and the (methyl) acryloyl chloride are expensive.
Disclosure of Invention
The technical problem to be solved by the invention is to overcome the defects of the prior art and provide a method for synthesizing adamantane (meth) acrylate.
In order to solve the technical problems, the invention provides the following technical scheme:
the invention provides a synthesis method of adamantane ester (meth) acrylate, which is carried out by the following reaction route:
wherein R is1Is hydrogen or methyl; r2Is an alkyl sulfonate; r3Is an alkane or cycloalkane; x1Is halogen; m is-MgX2Or Li, X2Is halogen;
the first step is as follows: reacting (methyl) acrylic acid with alkyl sulfonyl chloride to generate mixed anhydride S1;
the second step is that: under the action of a lithium reagent or a Grignard reagent, 2-adamantanone reacts with halogenated alkane to generate an intermediate S2;
the third step: the mixed anhydride S1 and the intermediate S2 react to form adamantane (meth) acrylate.
As a preferred embodiment of the present invention, the alkylsulfonate includes: p-toluenesulfonate, methanesulfonate and trifluoromethanesulfonate.
As the inventionAn optimized technical scheme, X1Is bromine or chlorine; x2Is bromine or chlorine.
The adamantane (meth) acrylate synthesized by the above synthesis method includes:
As a preferred technical solution of the present invention, the first step includes the steps of: 1 mol of (methyl) acrylic acid, 1-1.1 mol of alkyl sulfonyl chloride, 0.5-1.5% of polymerization inhibitor and a first solvent with the mass 7-10 times that of the (methyl) acrylic acid; cooling to 10-20 ℃, and dropwise adding 1-1.5 mol of organic base at 10-20 ℃; a large amount of solid is separated out; keeping the temperature at 10-20 ℃ for continuous reaction, and filtering to remove solids after the reaction is finished.
In a preferred embodiment of the present invention, when lithium is used as the reactive agent, the second step comprises the steps of: adding 0.9-1 mol of 2-adamantanone and a second solvent which is 5-10 times of the mass of the 2-adamantanone into a reaction bottle under the protection of inert gas, stirring and dissolving completely, cooling to 0-5 ℃, and adding 1.0-2.0 mol of halogenated alkane R2X, heating to 10-15 ℃, pouring 2.0-3.0 mol of metal lithium into a reaction bottle in batches, and adding lithium at the temperature of 10-20 ℃; and after the feeding is finished, stirring and reacting at 25-35 ℃.
In a preferred embodiment of the present invention, when magnesium is used as the reactant, the second step comprises the steps of: weighing 0.9-1 mol of 2-adamantanone, adding a second solvent which is 5-10 times of the mass of the 2-adamantanone into a reaction bottle under the protection of inert gas, cooling to 0-5 ℃, adding 2.0-3.0 mol of magnesium chips, and adding 1.0-3.0 mol of halogenated alkane R2X, after the temperature is increased to 10-15 ℃, dropwise adding weighed 2-adamantanone at the temperature of 10-20 ℃; and after the feeding is finished, stirring and reacting at 25-35 ℃.
As a preferred technical solution of the present invention, the third step includes the steps of: after the second step reaction, adding 0.05-0.5 mol of organic base and 0.5-1.5% of polymerization inhibitor into the reaction liquid in the second step, cooling to 0-5 ℃, slowly adding the reaction liquid filtered in the first step into the reaction liquid, keeping the temperature in the system at 0-5 ℃, and keeping the temperature at 0-10 ℃ for reaction.
As a preferred embodiment of the present invention, the first solvent and the second solvent each include: dichloromethane, chloroform, tetrahydrofuran, toluene, and N, N' -dimethylformamide.
As a preferred technical scheme of the invention, the organic base comprises triethylamine, diisopropylamine, pyridine or morpholine.
The polymerization inhibitor of the present invention comprises: p-tert-butylcatechol, p-hydroxyanisole and phenothiazine, hydroquinone, N-oxyl (nitroxide) polymerization inhibitor: 4-hydroxy TEMPO and 1, 6-hexamethylene-bis (N-formyl-N- (1-oxy-2, 2,6,6, -tetramethylpiperidin) -4-yl) amine and bis (2,2,6, 6-tetramethyl-4-piperidinyl) sebacate nitroxide free radicals.
The synthesis method of the invention also comprises the following post-treatment steps:
and after the third step of reaction is finished, filtering the reaction solution, concentrating at 20-35 ℃, adding 3-4 times of mass (compared with 2-adamantanone, the same below) of n-hexane, washing with 1-1.5 times of mass of water, separating out a large amount of viscous solids, and taking an upper organic phase by layering. The lower aqueous phase was back-extracted with n-hexane and the organic phases were combined. Adding 15% NaOH solution 1-1.5 times by mass, cleaning, layering, taking an upper organic phase, adding anhydrous sodium sulfate into the organic layer, drying, passing through silica gel 0.15-0.25 times by mass, washing the silica gel with n-hexane, and concentrating at 20-35 ℃. Adding 3-5 times of methanol for dissolving, adding activated carbon for decoloring and filtering, recrystallizing at-30 to-50 ℃ and low temperature, filtering to obtain a product, adding 0.2-0.3 times of mass of n-hexane for dissolving, adding 0.2-0.3 times of mass of water for washing for 2 times, adding anhydrous sodium sulfate for drying, adding 1-3% of a polymerization inhibitor, carrying out reduced pressure concentration at 20-30 ℃ to obtain a crude product, adding 1-3% of the polymerization inhibitor into the crude product, raising the temperature to 130-150 ℃, carrying out reduced pressure distillation, carrying out top temperature of 80-100 ℃, and connecting a main fraction, wherein the main fraction is adamantane (meth) acrylate.
Compared with the prior art, the invention has the following beneficial effects:
the invention provides a method for synthesizing adamantane ester (meth) acrylate, which provides more selectivity for synthesizing the adamantane ester (meth) acrylate. The synthesis method has the advantages of high yield, high product purity and low synthesis cost.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. In the drawings:
FIG. 1 is a schematic GC purity of 2-ethyl-2-adamantyl acrylate of example 1 of the present invention;
FIG. 2 is a schematic of the GC purity of 2-methyl-2-adamantyl methacrylate of example 2 of the present invention;
FIG. 3 is a schematic of the GC purity of 2-isopropyl-2-adamantyl acrylate of example 3 of the present invention.
Detailed Description
The preferred embodiments of the present invention will be described in conjunction with the accompanying drawings, and it will be understood that they are described herein for the purpose of illustration and explanation and not limitation.
Example 1
Step a: acrylic acid (200g), p-toluenesulfonyl chloride (530g), phenothiazine (2g) were added to methylene chloride (1500 g); cooling the dry ice ethanol bath to 15 ℃, and dropwise adding triethylamine (310g) at 15 +/-5 ℃; a large amount of solid is separated out; keeping the temperature at 15 +/-5 ℃ to continue reacting for 2 hours, and filtering to remove solids for later use after the reaction is finished;
step b: adding 2-adamantanone (410g) and tetrahydrofuran (2100g) into a reaction bottle under the protection of nitrogen, stirring and dissolving completely, cooling the mixture to 0 ℃ in a dry ice ethanol bath, introducing chloroethane (360g), heating to 10 ℃, pouring metal lithium (47g) into the reaction bottle in batches (adding the metal lithium into the reaction bottle in 5 batches within 4 hours), and controlling the temperature to be 10-20 ℃ to add the lithium; after the addition was complete, the solution was stirred overnight at 25 ℃ and gradually grayed. No lithium floated on the liquid surface, and it was confirmed that the reaction of lithium was substantially complete, and the solution was cloudy in gray.
Step c: triethylamine (28g) and phenothiazine (2g) were added to the reaction solution in step b, and the solution was cloudy in yellow-green color. And c, cooling to 5 ℃, dropwise adding the reaction liquid filtered in the step a into the reaction liquid, keeping the internal temperature at 0-5 ℃, keeping the color not to be obviously changed when dropwise adding, and keeping the temperature below 10 ℃ and stirring for 1 hour after dropwise adding is finished for 1.5 hours. The reaction solution was filtered through celite, concentrated at 25 ℃, added with n-hexane (1500g), washed with water (500g), to precipitate a large amount of viscous solid, and the upper organic phase was taken by layering. The lower aqueous phase was back-extracted with n-hexane (50g), the organic phases were combined, TLC confirmed the absence of product in the aqueous phase, washed with 15% NaOH solution (500g), and the upper organic phase was separated and greenish. The organic layer was dried over anhydrous sodium sulfate (50g), passed through a silica gel column (100g of silica gel), washed with n-hexane (50g), concentrated to dryness at 25 ℃ and then dried by oil pump. Adding methanol (2000g) for dissolution, adding active carbon (100g) for decolorization and filtration, recrystallizing at low temperature, cooling to-30 ℃, and starting crystallization. Continuously cooling to-50 ℃, and preserving heat for 1 hour. Filtering to obtain a product, adding n-hexane (100g) for dissolving, adding water (100g) for washing for 2 times, adding anhydrous sodium sulfate (50g) for drying, adding phenothiazine (10g), concentrating and drying at 25 ℃ under reduced pressure to obtain a light green crude product, supplementing phenothiazine (10g) to the crude product, raising the temperature to 135 ℃ for reduced pressure distillation, carrying out top temperature of 86-92 ℃, and collecting a main fraction to obtain 2-ethyl-2-adamantyl acrylate (434.5g, 67.9%, purity: 99.0%).
Example 2
Step a: methacrylic acid (200g), p-toluenesulfonyl chloride (443g), MEHQ (2g) was added to tetrahydrofuran (1500 g); cooling the dry ice ethanol bath to 15 ℃, and dropwise adding triethylamine (300g) at 15 +/-5 ℃; a large amount of solid is separated out; keeping the temperature at 15 +/-5 ℃ to continue reacting for 2 hours, and filtering to remove solids for later use after the reaction is finished;
step b: adding tetrahydrofuran (1700g) into a reaction bottle under the protection of nitrogen, cooling to 0 ℃, adding magnesium chips (125g), adding chloromethane (220g), heating to 15 ℃, and dropwise adding 2-adamantanone (332g) at 15 +/-5 ℃; and after the addition is finished, stirring and reacting for 3 hours at the temperature of 25-35 ℃.
Step c: triethylamine (24g) and MEHQ (2g) were added to the reaction solution in step b. And c, cooling to 5 ℃, dropwise adding the reaction liquid filtered in the step a into the reaction liquid, keeping the internal temperature at 0-5 ℃, dropwise adding after 1.5 hours, keeping the temperature below 10 ℃, and stirring for 1 hour. The reaction solution was filtered through celite, concentrated at 25 ℃, added with n-hexane (1300g), washed with water (450g), to precipitate a large amount of viscous solids, and the upper organic phase was taken by layering. The lower aqueous phase was back-extracted with n-hexane (45g), the organic phases were combined, TLC confirmed the absence of product in the aqueous phase, washed with 15% NaOH solution (450g), and the upper organic phase was taken after separation. The organic layer was dried over anhydrous sodium sulfate (45g), passed through a silica gel column (900g silica gel), washed with n-hexane (45g), concentrated to dryness at 25 ℃ and then dried by oil pump. Adding methanol (1800g) for dissolution, adding active carbon (100g) for decolorization and filtration, recrystallizing at low temperature, cooling to-30 ℃, and starting crystallization. Continuously cooling to-50 ℃, and preserving heat for 1 hour. Filtering to obtain a product, adding n-hexane (90g) for dissolving, adding water (90g) for washing for 2 times, adding anhydrous sodium sulfate (45g) for drying, adding MEHQ (9g), concentrating and drying at 25 ℃ under reduced pressure to obtain a crude product, supplementing MEHQ (9g) to the crude product, raising the temperature to 137 ℃ for reduced pressure distillation, carrying out top temperature of 87-95 ℃, and carrying out main fraction inoculation to obtain 2-methyl-2-adamantyl methacrylate (382g, 73.8%, purity: 99.6%).
Example 3
Step a: acrylic acid (200g), methanesulfonyl chloride (318g), phenothiazine (2g) were added to methylene chloride (1500 g); cooling the dry ice ethanol bath to 15 ℃, and dropwise adding triethylamine (310g) at 15 +/-5 ℃; a large amount of solid is separated out; keeping the temperature at 15 +/-5 ℃ to continue reacting for 2 hours, and filtering to remove solids for later use after the reaction is finished;
step b: adding 2-adamantanone (410g) and tetrahydrofuran (2100g) into a reaction bottle under the protection of nitrogen, stirring and dissolving completely, cooling to 0 ℃ in a dry ice ethanol bath, adding isopropyl bromide (336g), heating to 10 ℃, pouring metal lithium (47g) into the reaction bottle in batches (adding 5 batches in 4 hours), and adding lithium at the temperature of 10-20 ℃; after the addition was complete, the solution was gradually yellow with stirring overnight at 25 ℃. No lithium floated on the liquid surface, confirming that the lithium reaction was substantially complete.
Step c: triethylamine (28g) and phenothiazine (2g) were added to the reaction solution in step b. And c, cooling to 5 ℃, dropwise adding the reaction liquid filtered in the step a into the reaction liquid, keeping the internal temperature at 0-5 ℃, keeping the color not to be obviously changed when dropwise adding, and keeping the temperature below 10 ℃ and stirring for 1 hour after dropwise adding is finished for 1.5 hours. The reaction solution was filtered through celite, concentrated at 25 ℃, added with n-hexane (1500g), washed with water (500g), to precipitate a large amount of viscous solid, and the upper organic phase was taken by layering. The lower aqueous phase was back-extracted with n-hexane (50g), the organic phases were combined, TLC confirmed the absence of product in the aqueous phase, washed with 15% NaOH solution (500g), and the upper organic phase was separated and greenish. The organic layer was dried over anhydrous sodium sulfate (50g), passed through a silica gel column (100g of silica gel), washed with n-hexane (50g), concentrated to dryness at 25 ℃ and then dried by oil pump. Adding methanol (2000g) for dissolution, adding active carbon (100g) for decolorization and filtration, recrystallizing at low temperature, cooling to-30 ℃, and starting crystallization. Continuously cooling to-50 ℃, and preserving heat for 1 hour. Filtering to obtain a product, adding n-hexane (100g) for dissolving, adding water (100g) for washing for 2 times, adding anhydrous sodium sulfate (50g) for drying, adding phenothiazine (10g), concentrating and drying at 25 ℃ under reduced pressure to obtain a light green crude product, supplementing phenothiazine (10g) to the crude product, raising the temperature to 142 ℃, distilling under reduced pressure, carrying out top temperature to 90-95 ℃, and collecting a main fraction to obtain 2-isopropyl-2-adamantyl acrylate (480g, 70.8%, purity: 99.0%).
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A method for synthesizing adamantane (meth) acrylate, characterized in that the method is carried out by the following reaction scheme:
wherein R is1Is hydrogen or methyl; r2Is an alkyl sulfonate; r3Is an alkane or cycloalkane; x1Is halogen; m is-MgX2Or Li, X2Is halogen;
the first step is as follows: reacting (methyl) acrylic acid with alkyl sulfonyl chloride to generate mixed anhydride S1;
the second step is that: under the action of a lithium reagent or a Grignard reagent, 2-adamantanone reacts with halogenated alkane to generate an intermediate S2;
the third step: the mixed anhydride S1 and the intermediate S2 react to form adamantane (meth) acrylate.
2. The method for synthesizing adamantane (meth) acrylate according to claim 1, wherein the alkylsulfonate includes: p-toluenesulfonate, methanesulfonate and trifluoromethanesulfonate.
3. The method according to claim 1 or 2, wherein X is X1Is bromine or chlorine; x2Is bromine or chlorine.
4. The method according to claim 1 or 2, wherein the adamantane (meth) acrylate comprises:
5. The method for synthesizing adamantane (meth) acrylate according to claim 1 or 2, wherein the first step comprises the steps of: 1 mol of (methyl) acrylic acid, 1-1.1 mol of alkyl sulfonyl chloride, 0.5-1.5% of polymerization inhibitor and a first solvent with the mass 7-10 times that of the (methyl) acrylic acid; cooling to 10-20 ℃, and dropwise adding 1-1.5 mol of organic base at 10-20 ℃; a large amount of solid is separated out; keeping the temperature at 10-20 ℃ for continuous reaction, and filtering to remove solids after the reaction is finished.
6. The method for synthesizing adamantane (meth) acrylate according to claim 1 or 2, wherein when lithium is used as a reactive agent, the second step comprises the steps of: adding 0.9-1 mol of 2-adamantanone and a second solvent which is 5-10 times of the mass of the 2-adamantanone into a reaction bottle under the protection of inert gas, stirring and dissolving completely, cooling to 0-5 ℃, and adding 1.0-3.0 mol of halogenated alkane R2X, heating to 10-15 ℃, pouring 2.0-3.0 mol of metal lithium into a reaction bottle in batches, and adding lithium at the temperature of 10-20 ℃; and after the feeding is finished, stirring and reacting at 25-35 ℃.
7. The method according to claim 1 or 2, wherein the second step comprises the steps of, when magnesium is used as a reactive agent: weighing 0.9-1 mol of 2-adamantanone, adding a second solvent which is 5-10 times of the mass of the 2-adamantanone into a reaction bottle under the protection of inert gas, cooling to 0-5 ℃, adding 2.0-3.0 mol of magnesium chips, and adding 1.0-2.0 mol of halogenated alkane R2X, after the temperature is increased to 10-15 ℃, dropwise adding weighed 2-adamantanone at the temperature of 10-20 ℃; and after the feeding is finished, stirring and reacting at 25-35 ℃.
8. The method for synthesizing adamantane (meth) acrylate according to claim 1 or 2, wherein the third step comprises the steps of: after the second step reaction, adding 0.05-0.5 mol of organic base and 0.5-1.5% of polymerization inhibitor into the reaction liquid in the second step, cooling to 0-5 ℃, slowly adding the reaction liquid filtered in the first step into the reaction liquid, keeping the temperature in the system at 0-5 ℃, and keeping the temperature at 0-10 ℃ for reaction.
9. The method as claimed in claim 7, wherein the first solvent and the second solvent each comprise: dichloromethane, chloroform, tetrahydrofuran, toluene, and N, N' -dimethylformamide.
10. The method as claimed in claim 8, wherein the organic base includes triethylamine, diisopropylamine, pyridine and morpholine.
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| CN114315571A (en) * | 2021-12-27 | 2022-04-12 | 徐州博康信息化学品有限公司 | Preparation method of photoresist resin monomer |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004091402A (en) * | 2002-08-30 | 2004-03-25 | Mitsubishi Gas Chem Co Inc | Method for producing adamantyl acrylates |
| CN1537097A (en) * | 2001-08-01 | 2004-10-13 | ��ʽ�����ɽ | Process for producing acid anhydride |
| CN104230712A (en) * | 2014-09-26 | 2014-12-24 | 上海博康精细化工有限公司 | Method for preparing 2-isopropyl-2-adamantyl acrylate |
| CN104628557A (en) * | 2013-11-11 | 2015-05-20 | 徐州博康信息化学品有限公司 | Preparation method of 2-methyl-2-adamantyl acrylate |
| JPWO2013141127A1 (en) * | 2012-03-23 | 2015-08-03 | 大阪有機化学工業株式会社 | Method for producing adamantyl (meth) acrylate |
-
2020
- 2020-12-28 CN CN202011594985.7A patent/CN112812010A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1537097A (en) * | 2001-08-01 | 2004-10-13 | ��ʽ�����ɽ | Process for producing acid anhydride |
| JP2004091402A (en) * | 2002-08-30 | 2004-03-25 | Mitsubishi Gas Chem Co Inc | Method for producing adamantyl acrylates |
| JPWO2013141127A1 (en) * | 2012-03-23 | 2015-08-03 | 大阪有機化学工業株式会社 | Method for producing adamantyl (meth) acrylate |
| CN104628557A (en) * | 2013-11-11 | 2015-05-20 | 徐州博康信息化学品有限公司 | Preparation method of 2-methyl-2-adamantyl acrylate |
| CN104230712A (en) * | 2014-09-26 | 2014-12-24 | 上海博康精细化工有限公司 | Method for preparing 2-isopropyl-2-adamantyl acrylate |
Non-Patent Citations (1)
| Title |
|---|
| DAVID D. WIRTH: "Carboxylic Sulfonic Mixed Anhydrides: General Utility and Application to the Synthesis of Ceftazidime", 《TETRAHEDRON》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114315571A (en) * | 2021-12-27 | 2022-04-12 | 徐州博康信息化学品有限公司 | Preparation method of photoresist resin monomer |
| CN114315571B (en) * | 2021-12-27 | 2023-12-29 | 徐州博康信息化学品有限公司 | Preparation method of photoresist resin monomer |
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