CN1527810A - Method for producing 2-alkyl-2-adamantyl acrylate - Google Patents
Method for producing 2-alkyl-2-adamantyl acrylate Download PDFInfo
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- CN1527810A CN1527810A CNA028094875A CN02809487A CN1527810A CN 1527810 A CN1527810 A CN 1527810A CN A028094875 A CNA028094875 A CN A028094875A CN 02809487 A CN02809487 A CN 02809487A CN 1527810 A CN1527810 A CN 1527810A
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- Prior art keywords
- methyl
- alkyl
- acrylate
- adamantane radical
- reaction
- Prior art date
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Links
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 23
- -1 ester compound Chemical class 0.000 claims abstract description 61
- 238000006243 chemical reaction Methods 0.000 claims abstract description 42
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 32
- 229910052751 metal Inorganic materials 0.000 claims abstract description 18
- 239000002184 metal Substances 0.000 claims abstract description 18
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 125000005843 halogen group Chemical group 0.000 claims abstract description 8
- 125000004429 atom Chemical group 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 30
- 150000004703 alkoxides Chemical class 0.000 claims description 23
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 20
- 229910052799 carbon Inorganic materials 0.000 claims description 20
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 18
- DCUFMVPCXCSVNP-UHFFFAOYSA-N methacrylic anhydride Chemical compound CC(=C)C(=O)OC(=O)C(C)=C DCUFMVPCXCSVNP-UHFFFAOYSA-N 0.000 claims description 16
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 13
- CERQOIWHTDAKMF-UHFFFAOYSA-N alpha-methacrylic acid Natural products CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 9
- LDHQCZJRKDOVOX-UHFFFAOYSA-N 2-butenoic acid Chemical compound CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 claims description 6
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000005396 acrylic acid ester group Chemical group 0.000 claims 2
- 238000005886 esterification reaction Methods 0.000 abstract description 11
- 150000001875 compounds Chemical class 0.000 abstract description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 abstract description 7
- 125000004432 carbon atom Chemical group C* 0.000 abstract description 3
- ARJOQCYCJMAIFR-UHFFFAOYSA-N prop-2-enoyl prop-2-enoate Chemical compound C=CC(=O)OC(=O)C=C ARJOQCYCJMAIFR-UHFFFAOYSA-N 0.000 abstract description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 abstract 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 26
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 26
- 239000003795 chemical substances by application Substances 0.000 description 23
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- 239000007788 liquid Substances 0.000 description 17
- 230000009466 transformation Effects 0.000 description 15
- 239000002994 raw material Substances 0.000 description 14
- 229910000765 intermetallic Inorganic materials 0.000 description 13
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 13
- 239000012535 impurity Substances 0.000 description 11
- 230000032050 esterification Effects 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 238000004821 distillation Methods 0.000 description 8
- 238000004611 spectroscopical analysis Methods 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 150000001350 alkyl halides Chemical class 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 229910001623 magnesium bromide Inorganic materials 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 239000012044 organic layer Substances 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 4
- 150000001347 alkyl bromides Chemical class 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 150000002736 metal compounds Chemical class 0.000 description 4
- 238000007670 refining Methods 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000007818 Grignard reagent Substances 0.000 description 3
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 3
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 description 3
- 125000001246 bromo group Chemical group Br* 0.000 description 3
- 230000006837 decompression Effects 0.000 description 3
- 150000004795 grignard reagents Chemical class 0.000 description 3
- 230000002779 inactivation Effects 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- PAMIQIKDUOTOBW-UHFFFAOYSA-N 1-methylpiperidine Chemical compound CN1CCCCC1 PAMIQIKDUOTOBW-UHFFFAOYSA-N 0.000 description 2
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 150000001348 alkyl chlorides Chemical class 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- RDHPKYGYEGBMSE-UHFFFAOYSA-N bromoethane Chemical compound CCBr RDHPKYGYEGBMSE-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 150000002641 lithium Chemical class 0.000 description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 description 2
- 125000005395 methacrylic acid group Chemical group 0.000 description 2
- CCRIVCWOXSIYEP-UHFFFAOYSA-N methyl prop-2-enoate;hydrochloride Chemical compound Cl.COC(=O)C=C CCRIVCWOXSIYEP-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical compound [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 2
- MPPPKRYCTPRNTB-UHFFFAOYSA-N 1-bromobutane Chemical compound CCCCBr MPPPKRYCTPRNTB-UHFFFAOYSA-N 0.000 description 1
- MLRVZFYXUZQSRU-UHFFFAOYSA-N 1-chlorohexane Chemical compound CCCCCCCl MLRVZFYXUZQSRU-UHFFFAOYSA-N 0.000 description 1
- SQCZQTSHSZLZIQ-UHFFFAOYSA-N 1-chloropentane Chemical compound CCCCCCl SQCZQTSHSZLZIQ-UHFFFAOYSA-N 0.000 description 1
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 1
- MKVBKROQTVVURG-UHFFFAOYSA-N 2-chloro-2-methyladamantane Chemical compound C1C(C2)CC3CC1C(C)(Cl)C2C3 MKVBKROQTVVURG-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- 238000003747 Grignard reaction Methods 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 150000001263 acyl chlorides Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 230000002152 alkylating effect Effects 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- GZUXJHMPEANEGY-UHFFFAOYSA-N bromomethane Chemical compound BrC GZUXJHMPEANEGY-UHFFFAOYSA-N 0.000 description 1
- 244000309464 bull Species 0.000 description 1
- DVECBJCOGJRVPX-UHFFFAOYSA-N butyryl chloride Chemical compound CCCC(Cl)=O DVECBJCOGJRVPX-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 150000001805 chlorine compounds Chemical group 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000001143 conditioned effect Effects 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- NWFNSTOSIVLCJA-UHFFFAOYSA-L copper;diacetate;hydrate Chemical compound O.[Cu+2].CC([O-])=O.CC([O-])=O NWFNSTOSIVLCJA-UHFFFAOYSA-L 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001312 dry etching Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- BLCTWBJQROOONQ-UHFFFAOYSA-N ethenyl prop-2-enoate Chemical compound C=COC(=O)C=C BLCTWBJQROOONQ-UHFFFAOYSA-N 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- HVTICUPFWKNHNG-UHFFFAOYSA-N iodoethane Chemical compound CCI HVTICUPFWKNHNG-UHFFFAOYSA-N 0.000 description 1
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 1
- NXPHGHWWQRMDIA-UHFFFAOYSA-M magnesium;carbanide;bromide Chemical compound [CH3-].[Mg+2].[Br-] NXPHGHWWQRMDIA-UHFFFAOYSA-M 0.000 description 1
- VHRYZQNGTZXDNX-UHFFFAOYSA-N methacryloyl chloride Chemical compound CC(=C)C(Cl)=O VHRYZQNGTZXDNX-UHFFFAOYSA-N 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- PSHKMPUSSFXUIA-UHFFFAOYSA-N n,n-dimethylpyridin-2-amine Chemical compound CN(C)C1=CC=CC=N1 PSHKMPUSSFXUIA-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- TXSXJLMEOQAASX-UHFFFAOYSA-N phenyl but-2-enoate Chemical compound CC=CC(=O)OC1=CC=CC=C1 TXSXJLMEOQAASX-UHFFFAOYSA-N 0.000 description 1
- WRAQQYDMVSCOTE-UHFFFAOYSA-N phenyl prop-2-enoate Chemical compound C=CC(=O)OC1=CC=CC=C1 WRAQQYDMVSCOTE-UHFFFAOYSA-N 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The present invention relates to a method for producing a 2-alkyl-2-adamantyl acrylate, wherein a metal 2-alkyl-2-adamantylalkoxide compound (wherein the alkyl group is an alkyl group having 1 to 6 carbon atoms, the metal is a Li atom or-MgX, and X is a halogen atom) is reacted with an ester compound of acrylic anhydride or an alcohol having 2 to 8 carbon atoms and a double bond at the α and β positions and acrylic acid. The objective compound can be obtained at a higher conversion rate by adding a tertiary amine compound to the reaction system when the esterification reaction is carried out.
Description
Technical field
The present invention relates to as the useful 2-alkyl-2-adamantane radical base acrylate of the raw material of semiconductor resistor, and the manufacture method of 2-alkyl-2-adamantane radical ylmethyl acrylate (below, abbreviate these compounds as 2-alkyl-2-adamantane radical base (methyl) acrylate).
Background technology
With the resistance of alkyl adamantane esters such as alkyl adamantane (methyl) acrylate as the raw material manufacturing, known its dry etching patience height (for example the spy opens flat 5-265212 communique) in semiconductor fabrication process is paid close attention to the long-range nature of resistive material as semi-conductor.
Manufacture method as alkyl adamantane esters, be known that alkylating reagent that use is made of organometallic compound to 2-diamantane ketoalkylation, then with the metal alkyl adamantyl alkoxide that obtains by etheride esterification method (spy opens flat 10-182552 communique etc.).
Use in the above-mentioned esterification of (methyl) acrylate chloride as etheride, confirmed that any side reaction all can secondaryly generate muriate.This muriate is sneaked in the resistive material that makes as impurity, even mix the problem that also can have the performance that reduces resistive material when seldom measuring.Further, (methyl) acrylate chloride is because reactive high, and shortage prolonged preservation stability exists as reaction raw materials and uses difficult problem.
Summary of the invention
The object of the present invention is to provide a kind of manufacture method of halogenide such as (methyl) acryloyl halide of not using during to metal 2-alkyl-2-adamantane radical base alkoxide cpd (the following metallic compound that abbreviates as sometimes) esterification as 2-alkyl-2-adamantane radical base (methyl) acrylate of esterifying agent.According to this method, the secondary muriate that generates in the ester that makes fundamentally, the result can be suitable for the highly purified ester of purposes such as resistive material with high yield manufacturing.
The inventor has carried out all research for achieving the above object, found that, by use (methyl) acrylic anhydride or at α, alcohol and (methyl) the acrylic acid carboxylate of carbon number 2～8 that has two keys on the β position is as esterifying agent, can make the yield height and fundamentally not by-product give birth to muriatic, be applicable to 2-alkyl-2-adamantane radical base (methyl) acrylate of purposes such as resistance, and then finish the present invention.
Therefore, as described below for the present invention who achieves the above object.
[1] manufacture method of 2-alkyl-2-adamantane radical base (methyl) acrylate of following formula (2) expression, it is characterized in that, make the metal 2-alkyl-2-adamantane radical base alkoxide cpd of following formula (1) expression, with (methyl) acrylic anhydride or at α, pure and mild (methyl) the acrylic acid carboxylate reaction that has the carbon number 2～8 of two keys on the β position
(R
2Be hydrogen atom or methyl.)
{ R
1Be the alkyl of carbon number 1～6, M be the Li atom or-MgX (X represents halogen atom))
[2] according to the manufacture method of [1] described 2-alkyl-2-adamantane radical base (methyl) acrylate, wherein, the alkyl of metal 2-alkyl-2-adamantane radical base alkoxide cpd and 2-alkyl-2-adamantane radical base (methyl) acrylate is methyl or ethyl.
[3] manufacture method of basis [1] described 2-alkyl-2-adamantane radical base (methyl) acrylate, wherein, at α, the alcohol that has the carbon number 2～8 of two keys on the β position is (methyl) vinyl acrylate or the different propylene ester of (methyl) vinylformic acid with (methyl) acrylic acid carboxylate.
[4] according to [1] described manufacture method, it is characterized in that, make the metal 2-alkyl-2-adamantane radical base alkoxide cpd of following formula (1) expression, with (methyl) acrylic anhydride or at α, when having the acrylic acid carboxylate reaction of pure and mild (methyl) of carbon number 2～8 of two keys on the β position, there is 0.01～0.5 normal tertiary amine compound with respect to metal 2-alkyl-2-adamantane radical base alkoxide cpd.
Among the present invention, since make metal 2-alkyl-2-adamantane radical base alkoxide cpd, with (methyl) acrylic anhydride or at α, pure and mild (methyl) the acrylic acid carboxylate reaction that has the carbon number 2～8 of two keys on the β position is so can make 2-alkyl-2-adamantane radical base (methyl) acrylate expeditiously.In this manufacture method, because do not use the such chloride esterifying agent of acyl chlorides, so the secondary chloride content that generates is few in 2-alkyl-2-adamantane radical base (methyl) the propylene ester that obtains.Therefore, use the resistive performance height of its manufacturing.
In addition, can improve transformation efficiency by in reaction system, adding tertiary amine.
Embodiment
Below describe the present invention in detail.
(metallic compound)
The metallic compound of initial feed that is used for the part of manufacture method of the present invention is the metal 2-alkyl-2-adamantane radical base alkoxide cpd of following formula (1) expression.
Here, R
1Alkyl for carbon number 1～6.From use the high viewpoint of availability of the raw material of resistive material, R as semi-conductor
1The alkyl of carbon numbers 1～3 such as preferable methyl, ethyl, propyl group, sec.-propyl.Also can use the carbon number of alkyl to surpass 6 alkyl, but because be not easy to buy and carbon number surpasses 6 and do not bring special advantage, so preferred carbon number is in above-mentioned scope.
M represent the Li atom or-MgX.Here X represents halogen atom.As halogen atom, can enumerate fluorine atom, chlorine atom, bromine atoms, iodine atom.From the easiness of buying of metallic compound, preferred chlorine atom or bromine atoms are as halogen atom.Further from reactive viewpoint bromine atoms most preferably.
Can be fit to be used in the metallic compound of aforementioned formula of the present invention (1) expression, as the concrete example of magnesium halide 2-methyl-2-adamantyl alkoxide, can enumerate magnesium chloride 2-alkyl-2-adamantane radical base alkoxide cpd, magnesium bromide 2-methyl-2-adamantyl alkoxide cpd, magnesium chloride 2-ethyl-2-adamantyl alkoxide cpd, magnesium bromide 2-ethyl-2-adamantyl alkoxide cpd etc.
In these metallic compounds, from the viewpoint of the easiness made, preferred especially magnesium bromide 2-methyl-2-adamantyl alkoxide cpd.
Above-mentioned magnesium halide 2-alkyl-2-adamantane radical base alkoxide cpd can be made by 2-diamantane ketone and Grignard reagent simply.Grignard reaction itself is that those skilled in the art are known.
Raw material 2-diamantane ketone can directly use reagent or as industrial commercially available product, perhaps utilize refining back such as recrystallization, distillation to use them according to necessity.
The metallic compound that uses above-mentioned Grignard reagent manufacturing directly or it is filtered, cleans etc. according to necessity refining, then as the initial feed use of manufacture method of the present invention.
When this compound was lithium 2-alkyl-2-adamantane radical base alkoxide cpd, the metallic compound of aforementioned formula (1) expression can use with 2-diamantane ketone and lithium alkylide and pass through material that known the whole bag of tricks makes etc. as raw material.
This lithium 2-alkyl-2-adamantane radical base alkoxide cpd also can be modulated by aforesaid any means, but the method that illustrates below preferred especially.
That is the lithium 2-alkyl-2-adamantane radical base alkoxide cpd that obtains of solution by will containing 2-diamantane ketone and alkyl halide or suspension liquid (below, be also referred to as " organic raw material liquid ") and metallic lithium mixing direct reaction.
According to above-mentioned manufacture method, can be with yield acquisition object also high when using Grignard reagent.And because do not use, so needn't be subjected to high price and the chemically price of unsettled lithium alkylide and the puzzlement of the problem on the storage stability by other approach synthetic lithium alkylides.
Alkyl halide is with following formula (3) expression,
R
1-X????????????????(3)
(in the formula, R
1Be the alkyl of carbon number 1～6, X is a halogen atom.)
As alkyl halide, have no particular limits, can use alkyl bromide, alkiodide, alkyl chloride etc.From the easiness that raw material is bought, preferably have the alkyl chloride or the alkyl bromide of the alkyl of carbonatoms 1～6.From the high viewpoint of reactivity, preferred alkyl bromide or alkiodide.Specifically, but example Butyryl Chloride, amyl chloride, hexyl chloride, monobromomethane, monobromoethane, butyl bromide, methyl-iodide, iodoethane etc.
This puts from the transformation efficiency that improves 2-diamantane ketone, and this halid usage quantity represents to wish 2-diamantane ketone with mol ratio: alkylogen=1: 1～1: 1.2.
Solvent or dispersion agent as dissolving or disperse above-mentioned 2-diamantane ketone and alkyl halide can use relative metallic lithium, lithium alkylide and the stable organic solvent of alkoxyl group lithium.As these organic solvents, can lift ether solvents such as Anaesthetie Ether, tetrahydrofuran (THF), diox, varsol such as hexane, toluene and their mixed solvent etc.
The usage quantity of these organic solvents has no particular limits, and from the viewpoint of still yield, solubleness, speed of response, the concentration of preferably modulating 2-diamantane ketone is 0.01～10mol/l, especially preferably is modulated into 0.1～5mol/l.
As the method that makes the solution that contains 2-diamantane ketone and alkylogen or suspension (organic raw material liquid) mix, react, preferably organic raw material liquid is added lentamente to blended method in the suspension of metallic lithium with metallic lithium.According to this method, can control thermal value easily, also at first make the surface active of metallic lithium, so can react rapidly.
At this moment, as the shape of using metallic lithium, preferably use surface-area such as particulate state, laminar, finely particulate big, by using the metallic lithium of these shapes, speed of response will become greatly, and preferably.
In addition, the speed of adding above-mentioned organic raw material liquid in metallic lithium is different because of the kind of the alkylogen of use, cannot treat different things as the same.Preferably make temperature of reaction be no more than low arbitrarily-side in the boiling point of the boiling point of alkyl halide or used organic solvent, the interpolation speed of regulating organic raw material liquid.
Particularly alkyl halide is under the situation of iodide, preferably temperature of reaction is remained on to add organic stock liquid below 0 ℃.Can control side reaction like this.
When alkyl halide is under the situation of bromide, preferably satisfying above-mentioned condition, and the conditioned reaction temperature makes it the temperature more than 20 ℃ (that is to say an any low side's temperature in the boiling point of the boiling point of 20 ℃～alkyl bromide or used organic solvent), adds organic raw material liquid simultaneously.By such adjusting, can prevent the inactivation of metallic lithium.When dripping organic raw material liquid, preferably stir solvent.
The total addition level of metallic lithium has no particular limits.But from yield and the viewpoint that prevents the excessive use of metallic lithium, 1mol preferably adds 1.6～2.4 grammeatom to 2-diamantane ketone, preferred especially 1.8～2.2 grammeatom.
In addition, continuing under the situation of esterification described later, preferably making in the reaction solution after above-mentioned reaction is finished substantially not kish lithium.Therefore, the addition of metallic lithium preferably uses below 2 grammeatom with respect to 2-diamantane ketone 1mol, preferred especially 1.8～2.0 grammeatom.
The reaction times of abovementioned alkyl reaction because of the interpolation speed of metallic lithium and reaction heat to remove efficient etc. different, preferred 0.5～48 hour usually.In order to prevent the inactivation of metallic lithium, preferably under inert atmospheres such as argon, react.
By above-mentioned reaction, can obtain lithium 2-alkyl-2-adamantane radical base alkoxide cpd.
Among the present invention, can this lithium 2-alkyl-2-adamantane radical base alkoxide cpd be separated, make with extra care and use according to necessity.
(esterifying agent)
The other initial feed esterifying agent that uses as the present invention be following formula (4) expression (methyl) acrylic anhydride or following formula (5) expression at α, have alcohol and (methyl) acrylic acid carboxylate of the carbon number 2～8 of two keys on the β position.
Here, in formula (4), (5), R
2Expression hydrogen atom or methyl.R
3, R
4And R
5The expression hydrogen atom, alkyl or have the also passable aryl of substituting group, R
3With R
4Or R
4With R
5It is also passable to be interconnected to form ring-type.R
3, R
4And R
5Carbon number add up to 0～6.
As (methyl) acrylic anhydride of formula (4) expression, preferred acrylic anhydride, methacrylic anhydride.Also can use their mixed acid anhydride in addition.
As formula (5) expression at α, the alcohol and (methyl) acrylic acid carboxylate that have the carbon number 2～8 of two keys on the β position, but example (methyl) vinyl acrylate, the different propylene ester of (methyl) vinylformic acid, (methyl) vinylformic acid 1-tetrahydrobenzene ester, (methyl) vinylformic acid 2,6-dimethyl-1-tetrahydrobenzene ester, (methyl) vinylformic acid 1-phenylester, (methyl) phenyl acrylate, (methyl) vinylformic acid 4-nitro phenyl ester etc.From the aspect of buying easily, preferred especially (methyl) vinyl acrylate, the different propylene ester of (methyl) vinylformic acid, (methyl) phenyl acrylate.
These esterifying agents can use ad lib by known method synthetic esterifying agent.For example as the synthetic method of acid anhydrides; can enumerate the method for in methylene dichloride, using thionyl chloride as report in 4937 pages of No. 41, tetrahedoron letters in 1986 27 volumes, as shown in No. 247689, United States Patent (USP) in the presence of neutralized verdigris with the method for ethanoyl ketene reaction etc.In addition, adopt at α, the synthetic method that has the alcohol of carbon number 2～8 of two keys and (methyl) acrylic acid carboxylate on the β position is at the will C of Englishize association, 1986 years 2016 pages; Journal of Polymer Science, A-1, the 4th volume,, 1191 pages in 1966; Zh.Prikl.Khim. (Leningrad), 24,1951,851 (engl.Ausg.S.967,969); Zh.Obshch.Khim., 24,1954,450 (engl.Ausg.S.459); 851 pages of JACS the 83rd volumes 1961; Bull.Acad.Sci.USSR Div.Chem.Sci. (Engl.Transl.) 1967,2403 pages of grades are put down in writing to some extent.
These esterifying agents can be direct, perhaps is dissolved in the solvent, infeeds in the esterification described later.
(esterification)
Among the present invention, make the metallic compound of expression in the above-mentioned formula (1) and the esterifying agent reaction of formula (4) or formula (5) expression, make 2-alkyl-2-adamantane radical base (methyl) acrylate as formula (2) expression of purpose compound of the present invention.
This reaction is undertaken by mutual mixing above-claimed cpd.By using reaction soln can improve operation, control reaction temperature easily also.
As the solvent that uses in the reaction, so long as the solvent of metallizing thing and esterifying agent reaction not can use any solvent.Specifically, can the example ethyl ether, tetrahydrofuran (THF) (ether solvent such as THF), diox, varsols such as hexane, benzene,toluene,xylene, halogen series solvents such as methylene dichloride etc.
Preferred 0.01～the 10mol/l of the concentration of the metallic compound in the aforementioned solvents is from operating more preferably 0.1～5mol/l.
The amount of the esterifying agent that uses in the reaction is with respect to 1 mole preferred 0.9～1.3 mole of metallic compound.
The blending means of metallic compound and esterifying agent does not have specific restriction, in metal compound solution, add the method for esterifying agent or its solution, or it is all passable with the method for esterifying agent (or its solution) to add metallic compound (or its solution) in solvent respectively simultaneously.Wherein, the method for interpolation metal compound solution is preferred because of the polymerization of the purpose compound that can suppress to obtain in esterifying agent or its solution.
The situation that adds metal compound solution in esterifying agent or its solution, preferred limit control reaction temperature drips metal compound solution in a long time at every turn on a small quantity, continuously or off and on.Therefore, and different, the dropping time mostly was about 1～24 hour usually according to the size of making scale.
Reaction times is different because of the length that drips the time, and preferred usually the dropping finished back 0.5～6 hour.
Preferred-20～100 ℃ of the temperature of reaction of esterification is from taking into account speed of response and preventing in the polymerization preferred especially 0～40 ℃.
Viewpoint for the inactivation that prevents esterifying agent and metallic compound is reflected under the such inert atmosphere of nitrogen or argon gas and carries out.
Further, when esterification,, can more obtain carboxylate under the high conversion by in reaction system, adding tertiary amine compound.When in reaction system, adding primary amine and secondary amine, owing to react the generation acid amides with (methyl) acrylic acid carboxylate with (methyl) acrylic anhydride or alcohol as esterifying agent, so can not confirm the additive effect of amine.
Tertiary amine compound is not particularly limited, can use triethylamine, Tributylamine, N-methyl piperidine, N-methylmorpholine, 1,4-diazabicyclo [2.2.2] octane, 1,7-diazabicyclo [4.3.0] ninth of the ten Heavenly Stems-6-alkene, 1, aromatic nitrile base such as ring-type such as 8-diazabicyclo [5.4.0] 11-7-alkene or acyclic aliphatic tertiary amine or xylidene(s), pyridine, 4-dimethylaminopyridine.
The addition of this tertiary amine compound need not add equivalent with respect to metal 2-alkyl-2-adamantane radical base alkoxide cpd, and it is just enough to be generally 0.01 equivalent～0.5 equivalent.If littler than 0.01 equivalent, the additive effect of tertiary amine compound is low, adds the raising that can not find more than 0.5 equivalent than adding the also high transformation efficiency of 0.5 equivalent.
The addition means of this tertiary amine compound, interpolation are not subjected to influences such as the addition means of esterifying agent and temperature of reaction period, are arbitrarily.For example, behind hybrid metal 2-alkyl-2-adamantane radical base alkoxide cpd and the tertiary amine compound, make itself and esterifying agent react also passable.In addition, after metal 2-alkyl-2-adamantane radical base alkoxide cpd and the esterifying agent reaction, in reaction solution, react also passable again behind the adding tertiary amine compound.
In reaction system, the stopper that adds not metallizing thing reaction is also passable.As such stopper, can lift the stopper that does not have the phenol hydroxyl of thiodiphenylamine and so on.
After esterification finishes, when from reaction solution, reclaiming object, can use known various refining means.Specifically, but refining means such as example washing, solvent extraction, column chromatography, distillation, recrystallization.
Embodiment
Below, the present invention is described in detail for embodiment, but the present invention is not limited to these
Embodiment.
In addition, the transformation efficiency during esterification is calculated with following method.At first, reaction mixture is injected water, with the diethyl ether extraction, with the extraction liquid gc analysis that obtains.With gas chromatographic column obtain the peak area and total of 2-alkyl-2-adamantane radical alcohol (metal 2-alkyl-2-adamantane radical base alkoxide origin) as the peak area of 2-alkyl-2-adamantane radical base (methyl) acrylate of resultant, remove percentage that the peak area of 2-alkyl-2-adamantane radical base (methyl) acrylate calculates as transformation efficiency.
The theoretical amount of 2-alkyl-2-adamantane radical base (methyl) acrylate that the weight of yield by employed 2-diamantane ketone calculates is removed the percentage of the weight of isolating 2-alkyl-2-adamantane radical base (methyl) acrylate and is represented.
Embodiment 1
Under nitrogen atmosphere, in the flask of 500ml, put into 2-diamantane ketone 30g (0.2mol), add tetrahydrofuran (THF) (THF) 90g, make its dissolving.At this moment, be no more than 40 ℃ of THF solution (1.0mol/l) 220ml (0.22mol) that slowly drip commercially available methyl-magnesium-bromide down at reacting liquid temperature.Drip and finish back stirring 1 hour, obtain the THF solution of magnesium bromide 2-methyl-2-adamantyl alkoxide.Be no more than 40 ℃ at reacting liquid temperature then and slowly drip methacrylic anhydride 37g (0.24mol) down.After dripping end, at room temperature stir 4 hours (transformation efficiency 90%)., Yi Bian keep liquid temp 10 ℃ below, Yi Bian add methyl alcohol 10g and 10% aqueous sodium hydroxide solution 16g, stir 1 hour after, separate organic layer thereafter.After organic layer further washed with 10% aqueous sodium hydroxide washes, underpressure distillation removed and desolvates.The residue that obtains 85 ℃ to 90 ℃ distillations down, obtains 2-methyl-2-adamantyl methacrylic ester 23.0g (yield 49%) under the decompression of 0.3mmHg.When analyzing, do not detect chloride impurity with gas-chromatography-spectrometry mass (GC-MS).
Comparative example 1
Replace methacrylic anhydride, use methacrylic chloride, according to embodiment 1 Synthetic 2-methyl-2-adamantyl methacrylic ester.Transformation efficiency is 95%, and separation yield is 54.9%.When the compound that obtains is analyzed with gas-chromatography-spectrometry mass, detecting the impurity of thinking 2-chloro-2-methyl adamantane is 0.5%, also detect the not clear chloride impurity of 2 kinds of structures and be respectively 0.2% and 0.1%, also detect the not clear brominated impurity 0.1% of structure in addition.
Embodiment 2
Under nitrogen atmosphere, in the flask of 500ml, add THF30g, metallic lithium 2.78g (0.4mol).In this suspension, the control reacting liquid temperature is to drip the solution 90g that dissolves 2-diamantane ketone 30g (0.2mol) and monobromoethane 26.2g (0.24mol) in advance about 40 ℃ under nitrogen atmosphere.After dripping end reaction solution is warmed to 45 ℃, reacted slaking 1 hour.After the Visual Confirmation metallic lithium disappears, stirred 1 hour down at 45 ℃ again, obtain the solution of lithium 2-alkyl-2-adamantane radical base alkoxide.Reacting liquid temperature is kept below 40 ℃, on one side in this solution with 2 hours dropwise addition of acrylic acid acid anhydride 22.0g (0.21mol).After dripping end, at room temperature stirred slaking reaction (transformation efficiency 97%) 4 hours.
After the reaction slaking,,, stir after 1 hour, separate organic layer Yi Bian add methyl alcohol 10g and 10% aqueous sodium hydroxide solution 16g Yi Bian keep reacting liquid temperature below 10 ℃.After organic layer further washed with 10% aqueous sodium hydroxide washes, underpressure distillation removed and desolvates.The residue that obtains 80 ℃ to 85 ℃ distillations down, obtains 2-ethyl-2-adamantyl methacrylic ester 24.6g (yield 53%) under the decompression of 0.3mmHg.When it is analyzed with gas-chromatography-spectrometry mass, do not detect chloride impurity.
Embodiment 3～7
Replace methacrylic anhydride, use the compound shown in the table 1, according to embodiment 1 Synthetic 2-methyl-2-adamantyl (methyl) acrylate.Transformation efficiency, yield and as shown in table 1 with gas-chromatography-spectrometry mass analytical results to the compound that obtains.
Table 1
| Embodiment | Esterifying agent | Transformation efficiency (%) | Yield (%) | Chloride impurity (GC-MS) |
| ??3 | The methacrylic vinyl acetate | ??56.9 | ??33.3 | Do not detect |
| ??4 | The different propylene ester of methacrylic acid | ??66.6 | ??37.0 | Do not detect |
| ??5 | Methacrylic acid 2-phenylester | ??50.6 | ??35.0 | Do not detect |
| ??6 | Vinyl acrylate | ??65.1 | ??38.6 | Do not detect |
| ??7 | Phenyl acrylate | ??40.5 | ??29.1 | Do not detect |
Embodiment 8
According to embodiment 1, the THF solution of modulation magnesium bromide 2-methyl-2-adamantyl alkoxide.
Then, in the 500ml flask that adds methacrylic anhydride 37g (0.24mol) and THF100ml in advance, Yi Bian keep temperature to be no more than 40 ℃, Yi Bian slowly drip this THF solution.At room temperature stir 4 hours (transformation efficiency 91%) after dripping end.Then,,, stir after 1 hour, separate organic layer Yi Bian in reaction solution, add methyl alcohol 10g and 10% aqueous sodium hydroxide solution 16g Yi Bian keep reacting liquid temperature below 10 ℃.After organic layer further washed with 10% aqueous sodium hydroxide washes, underpressure distillation removed and desolvates.The residue that obtains 85 ℃ to 90 ℃ distillations down, obtains 2-methyl-2-adamantyl methacrylic ester 26.3g (yield 56%) under the decompression of 0.3mmHg.When it is analyzed with gas-chromatography-spectrometry mass, do not detect chloride impurity.
Embodiment 9
Replace methacrylic anhydride, use the methacrylic vinyl acetate, according to embodiment 8 Synthetic 2s-methyl-2-adamantane esters.The transformation efficiency of this moment is 70.0%, and yield is 34.0%.When analyzing this material, do not detect chloride impurity with gas-chromatography-spectrometry mass.
Embodiment 10
According to embodiment 1, bromizate magnesium 2-methyl-2-adamantyl alkoxide and methacrylic acid anhydride reactant.The transformation efficiency and embodiment 1 identical (90%) of this moment.At room temperature add triethylamine 2g (0.02mol, 0.1 equivalent) in this reaction solution, transformation efficiency brings up to 98% when stirring 2 hours.Carry out later processing according to embodiment 1, obtain 2-methyl-2-adamantyl methacrylic ester 26.2g (yield 56%).When analyzing this material, do not detect chloride impurity with gas-chromatography-spectrometry mass.
Embodiment 11
According to embodiment 1, the THF solution of modulation magnesium bromide 2-methyl-2-adamantyl alkoxide.At this moment, at room temperature add dimethyl aminopyridine 1.2g (0.01mol, 0.05 equivalent), Yi Bian keep temperature to be no more than 40 ℃ then, Yi Bian slow dropwise addition of acrylic acid acid anhydride.After dripping end, at room temperature stirred 2 hours.The transformation efficiency of this moment is 99%.Carry out later processing according to embodiment 1, obtain 2-methyl-2-adamantyl methacrylic ester 27.7g (yield 63%).When analyzing this material, do not detect chloride impurity with gas-chromatography-spectrometry mass.
Claims (4)
1. the manufacture method of 2-alkyl-2-adamantane radical base (methyl) acrylate of following formula (2) expression, it is characterized in that, make the metal 2-alkyl-2-adamantane radical base alkoxide cpd of following formula (1) expression, with (methyl) acrylic anhydride or at α, pure and mild (methyl) the acrylic acid ester cpds reaction that has the carbon number 2～8 of two keys on the β position
Wherein, R
2Be hydrogen atom or methyl,
Wherein, R
1The alkyl of carbon number 1～6, M be the Li atom or-MgX, X is a halogen atom.
2. the manufacture method of the described 2-alkyl-2-adamantane radical of claim 1 base (methyl) acrylate is characterized in that, the alkyl of metal 2-alkyl-2-adamantane radical base alkoxide cpd and 2-alkyl-2-adamantane radical base (methyl) acrylate is methyl or ethyl.
3. the manufacture method of the described 2-alkyl-2-adamantane radical of claim 1 base (methyl) acrylate, it is characterized in that, at α, the alcohol that has the carbon number 2～8 of two keys on the β position is (methyl) vinyl acrylate or the different propylene ester of (methyl) vinylformic acid with (methyl) acrylic acid ester cpds.
4. the manufacture method of the described 2-alkyl-2-adamantane radical of claim 1 ylmethyl acrylate, it is characterized in that, make the metal 2-alkyl-2-adamantane radical base alkoxide cpd of following formula (1) expression, with (methyl) acrylic anhydride or at α, when having the acrylic acid ester cpds reaction of pure and mild (methyl) of carbon number 2～8 of two keys on the β position, with respect to metal 2-alkyl-2-adamantane radical base alkoxide cpd, there is tertiary amine compound 0.01～0.5 equivalent.
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| JP172087/2001 | 2001-06-07 |
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| CN101811963A (en) * | 2009-02-20 | 2010-08-25 | 江苏大成医药化工有限公司 | Method for synthesizing photoresist-monomer carbon-rigid-skeleton acrylic ester compounds by transesterification |
| TWI460158B (en) * | 2008-12-26 | 2014-11-11 | Mitsubishi Gas Chemical Co | Method for producing adamantyl (meth)acrylates |
| 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 |
| CN104628562A (en) * | 2013-11-11 | 2015-05-20 | 傅志伟 | Preparation method for 2-ethyl-2-adamantanol acrylate |
| CN109232243A (en) * | 2018-10-16 | 2019-01-18 | 上海博栋化学科技有限公司 | The method that one kettle way prepares acrylic acid straight chained alkyl cyclohexyl |
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| JP2004315464A (en) * | 2003-04-18 | 2004-11-11 | Mitsubishi Gas Chem Co Inc | Method for producing adamantyl acrylate compound |
| JP4632759B2 (en) * | 2003-11-26 | 2011-02-16 | セントラル硝子株式会社 | Method for producing α-substituted norbornanyl acrylates |
| JP5124915B2 (en) * | 2005-07-12 | 2013-01-23 | 三菱瓦斯化学株式会社 | Process for producing 2-alkyl-2-adamantyl acrylates |
| WO2007094297A1 (en) * | 2006-02-15 | 2007-08-23 | Tokuyama Corporation | Method for producing polymerizable alkyl diamantyl ester compound |
| JP5993171B2 (en) * | 2012-03-23 | 2016-09-14 | 大阪有機化学工業株式会社 | Method for producing adamantyl (meth) acrylate |
| JP5918670B2 (en) * | 2012-09-20 | 2016-05-18 | 三新化学工業株式会社 | Method for producing acetylated sulfonium compound |
| JP6154737B2 (en) * | 2013-12-03 | 2017-06-28 | 大阪有機化学工業株式会社 | Method for producing cycloaliphatic acrylates |
| US20210108009A1 (en) * | 2019-10-14 | 2021-04-15 | Songwon Industrial Co., Ltd. | Method for producing alicyclic acrylate derivative |
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| JPH01238362A (en) | 1988-03-18 | 1989-09-22 | Sharp Corp | Telephone set with emergency information function |
| JP2000038362A (en) * | 1998-07-22 | 2000-02-08 | Tokuyama Corp | Production of sublimable adamantanol |
| JP2000229911A (en) * | 1999-02-05 | 2000-08-22 | Mitsubishi Rayon Co Ltd | Production of 2-alkyl-2-adamantyl (meth)acrylates |
| JP2000309558A (en) * | 1999-02-22 | 2000-11-07 | Sumitomo Chem Co Ltd | Production of 2-adamanthyl(meth)acrylate compound |
| JP4372281B2 (en) * | 1999-09-28 | 2009-11-25 | ダイセル化学工業株式会社 | Adamantane derivative and process for producing the same |
| JP2002003448A (en) * | 2000-06-20 | 2002-01-09 | Tokuyama Corp | Method of producing 2-alkyl-2-adamantyl (meth)acrylate |
| EP1314713A4 (en) * | 2000-07-27 | 2005-10-05 | Tokuyama Corp | Processes for preparation of 2-alkyl-2-adamantyl esters |
| US6521781B2 (en) * | 2000-12-15 | 2003-02-18 | Mitsubishi Gas Chemical Company, Inc. | Production of 2-hydrocarbyl-2-adamantyl acrylate compounds |
-
2002
- 2002-06-05 KR KR1020037015919A patent/KR100724672B1/en not_active IP Right Cessation
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| CN104628562A (en) * | 2013-11-11 | 2015-05-20 | 傅志伟 | Preparation method for 2-ethyl-2-adamantanol 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 |
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| TWI245757B (en) | 2005-12-21 |
| JP2003055301A (en) | 2003-02-26 |
| WO2002100816A1 (en) | 2002-12-19 |
| JP2006335766A (en) | 2006-12-14 |
| JP3868335B2 (en) | 2007-01-17 |
| KR100724672B1 (en) | 2007-06-07 |
| KR20040014548A (en) | 2004-02-14 |
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