JPH0479889A - Production of acrylic acid or methacrylic acid alkylaminoalkyl ester - Google Patents
Production of acrylic acid or methacrylic acid alkylaminoalkyl esterInfo
- Publication number
- JPH0479889A JPH0479889A JP19072790A JP19072790A JPH0479889A JP H0479889 A JPH0479889 A JP H0479889A JP 19072790 A JP19072790 A JP 19072790A JP 19072790 A JP19072790 A JP 19072790A JP H0479889 A JPH0479889 A JP H0479889A
- Authority
- JP
- Japan
- Prior art keywords
- ester
- acrylic acid
- enzyme
- methacrylic acid
- alkylaminoalkyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- -1 methacrylic acid alkylaminoalkyl ester Chemical class 0.000 title claims abstract description 21
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 title claims description 24
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 title claims description 22
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract description 22
- 150000002148 esters Chemical class 0.000 claims abstract description 22
- 102000004190 Enzymes Human genes 0.000 claims abstract description 21
- 108090000790 Enzymes Proteins 0.000 claims abstract description 21
- 244000005700 microbiome Species 0.000 claims abstract description 10
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 3
- 241000235395 Mucor Species 0.000 claims abstract 2
- 241000235527 Rhizopus Species 0.000 claims abstract 2
- 238000000034 method Methods 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 238000005809 transesterification reaction Methods 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 241000590020 Achromobacter Species 0.000 claims 1
- 241000588986 Alcaligenes Species 0.000 claims 1
- 241000228212 Aspergillus Species 0.000 claims 1
- 241000193830 Bacillus <bacterium> Species 0.000 claims 1
- 241000222120 Candida <Saccharomycetales> Species 0.000 claims 1
- 241000589516 Pseudomonas Species 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 13
- 239000006227 byproduct Substances 0.000 abstract description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 3
- 239000000047 product Substances 0.000 abstract description 3
- 125000004185 ester group Chemical group 0.000 abstract 2
- 230000003301 hydrolyzing effect Effects 0.000 abstract 2
- 241000233866 Fungi Species 0.000 abstract 1
- 238000009970 yarn dyeing Methods 0.000 abstract 1
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 8
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- DPBJAVGHACCNRL-UHFFFAOYSA-N 2-(dimethylamino)ethyl prop-2-enoate Chemical compound CN(C)CCOC(=O)C=C DPBJAVGHACCNRL-UHFFFAOYSA-N 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 4
- 229960002887 deanol Drugs 0.000 description 4
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000000278 alkyl amino alkyl group Chemical group 0.000 description 3
- 238000004587 chromatography analysis Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- XWJBRBSPAODJER-UHFFFAOYSA-N 1,7-octadiene Chemical compound C=CCCCCC=C XWJBRBSPAODJER-UHFFFAOYSA-N 0.000 description 2
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical compound CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- RYPKRALMXUUNKS-UHFFFAOYSA-N 2-Hexene Natural products CCCC=CC RYPKRALMXUUNKS-UHFFFAOYSA-N 0.000 description 2
- QQZOPKMRPOGIEB-UHFFFAOYSA-N 2-Oxohexane Chemical compound CCCCC(C)=O QQZOPKMRPOGIEB-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- CATSNJVOTSVZJV-UHFFFAOYSA-N heptan-2-one Chemical compound CCCCCC(C)=O CATSNJVOTSVZJV-UHFFFAOYSA-N 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methylcyclopentane Chemical compound CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- UALKQROXOHJHFG-UHFFFAOYSA-N 1-ethoxy-3-methylbenzene Chemical compound CCOC1=CC=CC(C)=C1 UALKQROXOHJHFG-UHFFFAOYSA-N 0.000 description 1
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 1
- IWSZDQRGNFLMJS-UHFFFAOYSA-N 2-(dibutylamino)ethanol Chemical compound CCCCN(CCO)CCCC IWSZDQRGNFLMJS-UHFFFAOYSA-N 0.000 description 1
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 description 1
- BFSVOASYOCHEOV-UHFFFAOYSA-N 2-diethylaminoethanol Chemical compound CCN(CC)CCO BFSVOASYOCHEOV-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- VCUFZILGIRCDQQ-KRWDZBQOSA-N N-[[(5S)-2-oxo-3-(2-oxo-3H-1,3-benzoxazol-6-yl)-1,3-oxazolidin-5-yl]methyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C1O[C@H](CN1C1=CC2=C(NC(O2)=O)C=C1)CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F VCUFZILGIRCDQQ-KRWDZBQOSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- YFNONBGXNFCTMM-UHFFFAOYSA-N butoxybenzene Chemical compound CCCCOC1=CC=CC=C1 YFNONBGXNFCTMM-UHFFFAOYSA-N 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 description 1
- OWMBTIRJFMGPAC-UHFFFAOYSA-N dimethylamino 2-methylprop-2-enoate Chemical compound CN(C)OC(=O)C(C)=C OWMBTIRJFMGPAC-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 229940069096 dodecene Drugs 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- LIKMAJRDDDTEIG-UHFFFAOYSA-N n-hexene Natural products CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000013054 paper strength agent Substances 0.000 description 1
- XNLICIUVMPYHGG-UHFFFAOYSA-N pentan-2-one Chemical compound CCCC(C)=O XNLICIUVMPYHGG-UHFFFAOYSA-N 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 150000003752 zinc compounds Chemical class 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、アクリル酸またはメタクリル酸のアルキルア
ミノアルキルエステルの製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing alkylaminoalkyl esters of acrylic acid or methacrylic acid.
アクリル酸またはメタクリル酸のアルキルアミノアルキ
ルエステルは、分子内にアミノ基を有しているため、繊
維の染色性改質剤、プラスチックの静電防止剤等として
、またこれらのモノマーを重合・共重合させたポリマー
は、紙力増強剤、トナーバインダー、紫外線硬化印刷用
材料、染料用樹脂、高分子凝集側及びイオン交換樹脂等
として有用である。Alkylaminoalkyl esters of acrylic acid or methacrylic acid have amino groups in their molecules, so they can be used as dyeing modifiers for fibers, antistatic agents for plastics, etc., and these monomers can be polymerized and copolymerized. The resulting polymers are useful as paper strength agents, toner binders, ultraviolet curing printing materials, resins for dyes, polymer agglomerates, ion exchange resins, and the like.
既に、アクリル酸またはメタクリル酸の低級工ステル（
ここでいう「低級エステル」とは、炭］数が１〜４のア
ルキル基を有するエステルであｔ以下で使用する「低級
エステル」もこの定義に。Already, lower synthetic esters of acrylic acid or methacrylic acid (
The term "lower ester" as used herein refers to an ester having an alkyl group having a carbon number of 1 to 4, and the "lower ester" used below t is also included in this definition.
る）とアルキルアミノアルキルアルコールの工；チル交
換反応によりアクリル酸またはメタクリル酸のアルキル
アミノアルキルエステルをｌＪ造ｔ；。) and alkylaminoalkyl alcohol; production of alkylaminoalkyl esters of acrylic acid or methacrylic acid by a chill exchange reaction;
方法は公知であり、触媒として、アルカリ金属フルコラ
ート、アルミニウムアルコラード、チタシアルコラート
、ジプチル錫オキサイド等の有機側化合物または亜鉛塩
類や亜鉛キレート錯体無水老等の亜鉛化合物を用いるこ
とが知られている。The method is known, and it is known to use organic compounds such as alkali metal flucorate, aluminum alcoholate, titanium alcoholate, and diptyltin oxide, or zinc compounds such as zinc salts and zinc chelate complexes anhydrous. .
〔発明が解決しようとするＩｆｆ）
しかしながら、触媒としてアルカリ金属アルニラート蜂
を用いた場合には、反応中または反応彷目的物を蒸留す
る過程で原料アクリル酸またはメタクリル酸の低級エス
テル及び、生成するアクリル酸またはメタクリル酸のア
ルキルアミノアルキルエステルの二重結合部への原料の
アルキルアミノアルキルアルコールまたは反応で副生ず
る低級アルコールの付加する反応がおこりやすく、目的
物の収率および純度を低下させるという欠点がある。こ
の欠点は、特に顕著にアクリル酸エステルのエステル交
換に現れ、メタクリル酸エステルの場合には使用できる
触媒でもアクリル酸エステルの場合には使用できないこ
とが多い。[If to be solved by the invention] However, when an alkali metal alnylate bee is used as a catalyst, lower esters of raw material acrylic acid or methacrylic acid and the produced acrylic acid are The drawback is that addition of raw material alkylaminoalkyl alcohol or lower alcohol by-produced in the reaction to the double bond of the alkylaminoalkyl ester of acid or methacrylic acid tends to occur, reducing the yield and purity of the target product. be. This drawback is particularly noticeable in the transesterification of acrylic esters, and even though catalysts can be used for methacrylic esters, they often cannot be used for acrylic esters.
本発明者らは、前述の欠点を解決するため、鋭意検討し
た結果、エステルを不斉水解する能力を有する酵素又は
微生物を用いることにより前述の欠点を克服できること
を見出し、本発明を完成するに至った。In order to solve the above-mentioned drawbacks, the present inventors have made extensive studies and found that the above-mentioned drawbacks can be overcome by using enzymes or microorganisms that have the ability to asymmetrically hydrolyze esters, and have completed the present invention. It's arrived.
すなわち、本発明は、一般式（１）
％式％（）
（式中、Ｒ１は水素またはメチル基、６は炭素数１〜４
のアルキル基を示す）で表されるアクリル酸またはメタ
クリル酸の低級エステルと一般式（ｆｆ）ＲＪａＮ（Ｃ
Ｈｚ）ｎｏｔ（（ＩＩ ）（式中、ＲＩ Ｒ４はそれぞ
れ独立に水素または炭素数１〜６のアルキル基、ｎは２
〜６の整数を示すす）で表されるアルキルアミノアルキ
ルアルコールとのエステル交換反応によりアクリル酸ま
たはメタクリル酸のアルキルアミノアルキルエステルを
製造するに際して、エステルを不斉水解する能力を有す
る酵素又は微生物を用いることを特徴とするアクリル酸
またはメタクリル酸のアルキルアミノアルキルエステル
の製造方法である。That is, the present invention is based on the general formula (1) % formula % () (wherein R1 is hydrogen or a methyl group, 6 is a carbon number of 1 to 4
(representing an alkyl group) and a lower ester of acrylic acid or methacrylic acid represented by the general formula (ff) RJaN (C
Hz) not ((II) (wherein, RI R4 is each independently hydrogen or an alkyl group having 1 to 6 carbon atoms, n is 2
When producing an alkylaminoalkyl ester of acrylic acid or methacrylic acid by a transesterification reaction with an alkylaminoalkyl alcohol represented by an integer of ~6, enzymes or microorganisms having the ability to asymmetrically hydrolyze the ester are used. This is a method for producing an alkylaminoalkyl ester of acrylic acid or methacrylic acid.
以下、本発明の方法を詳細に説明する。The method of the present invention will be explained in detail below.
本発明の方法は、アクリル酸またはメタクリル酸の低級
エステルとアルキルアミノアルキルアルコールと酵素又
は微生物の混合液を攪拌して反応を進め、目的のアクリ
ル酸またはメタクリル酸のアルキルアミノアルキルエス
テルを製造する方法である０例えば、アクリル酸メチル
とジメチルアミノエタノールを原料として使用し、ジメ
チルアミノエチルアクリレートを製造する場合、本エス
テル交換反応は、次式で示される。The method of the present invention is a method for producing the target alkylaminoalkyl ester of acrylic acid or methacrylic acid by stirring a mixture of a lower ester of acrylic acid or methacrylic acid, an alkylaminoalkyl alcohol, and an enzyme or a microorganism to advance the reaction. For example, when dimethylaminoethyl acrylate is produced using methyl acrylate and dimethylaminoethanol as raw materials, the transesterification reaction is represented by the following formula.
ＣＴｏ ＝ＣＨＣ００Ｃｔ１．＋（ＣＨｉ） ＊ＮＣＨ
ｔＣＨｘＯＨ→Ｃｕｔ −ＣＨＣＯＯＣｌｉｚＣＨＪ
（ＣＨｓ） ｔ ＋ＣＨ３０Ｈ本発明の方法として用い
られるアルキルアミノアルキルアルコールとしては、例
えば、ジメチルアミノエタノール、ジエチルアミノエタ
ノール、ジブチルアミノエタノールなどを挙げることが
できる。また、アクリル酸またはメタクリル酸の低級エ
ステルとしては、例えば、アクリル酸メチル、アクリル
酸エチル、アクリル酸ブチル、メタクリル酸メチルなど
を挙げることができる。アクリル酸またはメタクリル酸
の低級エステルの使用量は、アルキルアミノアルキルア
ルコールに対して通常０．５〜１０倍モル、好ましくは
１．０〜５倍モルである。CTo=CHC00Ct1. +(CHi) *NCH
tCHxOH→Cut -CHCOOClizCHJ
(CHs) t +CH30H Examples of the alkylaminoalkyl alcohol used in the method of the present invention include dimethylaminoethanol, diethylaminoethanol, dibutylaminoethanol, and the like. Examples of lower esters of acrylic acid or methacrylic acid include methyl acrylate, ethyl acrylate, butyl acrylate, and methyl methacrylate. The amount of the lower ester of acrylic acid or methacrylic acid to be used is usually 0.5 to 10 times the mole, preferably 1.0 to 5 times the mole relative to the alkylaminoalkyl alcohol.
本発明に用いることのできる酵素は、エステルを不斉水
解する能力を有する酵素であり、例えば表１に示した酵
素を挙げることができる。Enzymes that can be used in the present invention are enzymes that have the ability to asymmetrically hydrolyze esters, and include, for example, the enzymes shown in Table 1.
また、本方法に用いることのできる微生物は、例えば、
表１の「起源」の項に示した微生物を挙げることができ
る。In addition, microorganisms that can be used in this method include, for example,
The microorganisms shown in the "Origin" section of Table 1 can be mentioned.
表
本発明の方法の実施に当って、反応溶媒として原料のア
クリル酸、メタクリル酸の低級エステル及びアルキルア
ミノアルキルアルコールそのものを用いることができる
が、必要に応して有機溶媒を用いることができる。次に
、有ｆｍｆ４媒の具体例を示す。脂肪族炭化水素類とし
てはペンタン、ヘキサン、ヘプタン、オクタン、イソオ
クタン、ノナン、デカン、ｌ−または２−ヘキセン、１
−オクテン、１−ドデセン、ｌ、３−ペンタジェン、１
．５−へキサジエン、１．７−オクタジエン等が、脂環
式炭化水素類としてはシクロペンタン、シクロヘキサン
、メチルシクロペンタン、メチルシクロヘキサン等が、
芳香族炭化水素類としてはトルエン、キシレン、スチレ
ン、エチルベンゼン、クロルベンゼン等が、エーテル類
としてはｍ−ヘキシルエーテル、ｎ−ブチルフェニルエ
ーテル、ジフェニルエーテル、ジフェニルエーテル、メ
トキシトルエン等が、ケトン類としては２−ペンタノン
、２−ヘキサノン、２−ヘプタノン、シクロヘキサノン
等がそれぞれ挙げられる。Table In carrying out the method of the present invention, the raw materials, lower esters of acrylic acid and methacrylic acid, and alkylaminoalkyl alcohols themselves can be used as reaction solvents, but organic solvents can also be used if necessary. Next, a specific example of the fmf4 medium will be shown. Aliphatic hydrocarbons include pentane, hexane, heptane, octane, isooctane, nonane, decane, 1- or 2-hexene, 1
-octene, 1-dodecene, l,3-pentadiene, 1
．． 5-hexadiene, 1,7-octadiene, etc., and alicyclic hydrocarbons include cyclopentane, cyclohexane, methylcyclopentane, methylcyclohexane, etc.
Examples of aromatic hydrocarbons include toluene, xylene, styrene, ethylbenzene, and chlorobenzene; examples of ethers include m-hexyl ether, n-butylphenyl ether, diphenyl ether, diphenyl ether, and methoxytoluene; and examples of ketones include 2- Examples include pentanone, 2-hexanone, 2-heptanone, and cyclohexanone.
また有機溶媒単独でも反応は進むが、水分を添加するこ
とにより反応が加速される場合があるので、必要に応じ
て０．０１−１０％の水を添加する。Further, although the reaction proceeds with an organic solvent alone, the reaction may be accelerated by adding water, so 0.01-10% water is added as necessary.
かくして数時間から数日間、攪拌又は振とうを行なう０
反応は５〜１００℃で実施できるが、低温では反応が遅
くなり、高温では酵素の失活が見られることがあるので
、１０〜５０℃が望ましい。Thus, stirring or shaking is required for several hours to several days.
The reaction can be carried out at a temperature of 5 to 100°C, but a temperature of 10 to 50°C is desirable since the reaction slows down at low temperatures and deactivation of the enzyme may be observed at high temperatures.
反応終了後、反応液より減圧下にまず未反応のアクリル
酸またはメタクリル酸の低級エステルを留去せしめて、
目的物であるアクリル酸またはメタクリル酸のアルキル
アミノアルキルエステルを得る。目的物は、蒸留等によ
り精製しガスクロマトグラフィーにより確認した。After the reaction is completed, unreacted lower esters of acrylic acid or methacrylic acid are first distilled off from the reaction solution under reduced pressure.
The desired alkylaminoalkyl ester of acrylic acid or methacrylic acid is obtained. The target product was purified by distillation etc. and confirmed by gas chromatography.
以下、実施例により、本発明の方法を具体的に説明する
。Hereinafter, the method of the present invention will be specifically explained with reference to Examples.
実施例１
表２に示した酵素１０■をアクリル酸メチル１．０ｇに
添加し、さらにジメチルアミノエタノール０．９ｇを添
加した。その後、２２℃にて３時間振とうした。Example 1 10 μg of the enzyme shown in Table 2 was added to 1.0 g of methyl acrylate, and further 0.9 g of dimethylaminoethanol was added. Thereafter, it was shaken at 22°C for 3 hours.
生成したジメチルアミノエチルアクリレートをガスクロ
マトグラフ分析により測定した。いずれの酵素を用いて
も副生物であるジメチルアミノエチルアクリレートの二
重結合部への付加物は無かった。Dimethylaminoethyl acrylate produced was measured by gas chromatographic analysis. No matter which enzyme was used, there was no addition of the by-product dimethylaminoethyl acrylate to the double bond.
実施例２
表２に示した酵素１０■をメタアクリル酸エチルｉ、ｏ
ｇに添加し、以下実施例１と同様の操作を行った。生
成したジメチルアミノエチルメタアクリレートをガスク
ロマトグラフ分析により測定した。Example 2 Enzyme 10 shown in Table 2 was mixed with ethyl methacrylate i, o
g, and the same operation as in Example 1 was performed. Dimethylaminoethyl methacrylate produced was measured by gas chromatographic analysis.
いずれの酵素を用いても副生物であるジメチルアミノメ
タアクリレートの二重結合部への付加物は無かった。No matter which enzyme was used, there was no addition of the by-product dimethylaminomethacrylate to the double bond.
実施例３
表３に示す酵素１０■にヘキサン２ｄを加え、その後ア
クリル酸メチル０．０５ ｇに添加し、さらにジメチル
アミノエタノール０．０４５ｇを添加した。更に水含量
がそれぞれ０〜１０重量％になるように水を添加し、そ
の後、２２℃にて３時間振とうした。Example 3 2 d of hexane was added to 10 ml of the enzyme shown in Table 3, followed by 0.05 g of methyl acrylate, and further 0.045 g of dimethylaminoethanol. Further, water was added so that the water content was 0 to 10% by weight, and then the mixture was shaken at 22°C for 3 hours.
生成したジメチルアミノエチルアクリレートをガスクロ
マトグラフ分析により測定した。いずれの酵素を用いて
も副生物であるジメチルアミノエチルアクリレートの二
重結合部への付加物は無かった。Dimethylaminoethyl acrylate produced was measured by gas chromatographic analysis. No matter which enzyme was used, there was no addition of the by-product dimethylaminoethyl acrylate to the double bond.
エステルを不斉水解する能力を有する酵素又は微生物を
用いることにより、生成するアクリル酸またはメタクリ
ル酸のアルキルアミノアルキルエステルの二重結合部へ
の原料のアルキルアミノアルキルアルコールまたは反応
で副生する低級アルコールの付加反応物の副生なしに、
収率よく目的のアクリル酸またはメタクリル酸のアルキ
ルアミノアルキルエステルを製造する事ができた。By using enzymes or microorganisms that have the ability to asymmetrically hydrolyze esters, alkylaminoalkyl alcohol as a raw material or lower alcohol as a by-product in the reaction is added to the double bond of alkylaminoalkyl ester of acrylic acid or methacrylic acid. without the by-product of the addition reactant of
The desired alkylaminoalkyl ester of acrylic acid or methacrylic acid could be produced with good yield.
これは酵素のもつ反応特異性の高さに起因すると考えら
れる。This is thought to be due to the high reaction specificity of the enzyme.
Claims (2)
１〜４のアルキル基を示す）で表されるアクリル酸また
はメタクリル酸の低級エステルと一般式（II）Ｒ＿３Ｒ
＿４Ｎ（ＣＨ＿２）ｎＯＨ（II） （式中、Ｒ＿３、Ｒ＿４はそれぞれ独立に水素または炭
素数１〜６のアルキル基、ｎは２〜６の整数を示す）で
表されるアルキルアミノアルキルアルコールとのエステ
ル交換反応によりアクリル酸またはメタクリル酸のアル
キルアミノアルキルエステルを製造するに際して、エス
テルを不斉水解する能力を有する酵素又は微生物を用い
ることを特徴とするアクリル酸またはメタクリル酸のア
ルキルアミノアルキルエステルの製造方法。(1) Lower ester of acrylic acid or methacrylic acid represented by the general formula (I) CH_2=CR_1COOR_2 (I) (in the formula, R_1 is hydrogen or a methyl group, and R_2 is an alkyl group having 1 to 4 carbon atoms) and general formula (II) R_3R
with an alkylaminoalkyl alcohol represented by _4N(CH_2)nOH(II) (wherein R_3 and R_4 are each independently hydrogen or an alkyl group having 1 to 6 carbon atoms, and n is an integer of 2 to 6). Production of an alkylaminoalkyl ester of acrylic acid or methacrylic acid, characterized in that an enzyme or microorganism having the ability to asymmetrically hydrolyze the ester is used in producing the alkylaminoalkyl ester of acrylic acid or methacrylic acid by a transesterification reaction. Method.
、カンジダ属、シュードモナス属、アルカリゲネス属、
アクロモバクター属、バチルス属の各属に属する微生物
に由来のものである、特許請求の範囲第（１）項に記載
の方法。(2) The enzyme is Rhizopus, Mucor, Aspergillus, Candida, Pseudomonas, Alcaligenes,
The method according to claim (1), which is derived from microorganisms belonging to the genus Achromobacter and Bacillus.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19072790A JPH0479889A (en) | 1990-07-20 | 1990-07-20 | Production of acrylic acid or methacrylic acid alkylaminoalkyl ester |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19072790A JPH0479889A (en) | 1990-07-20 | 1990-07-20 | Production of acrylic acid or methacrylic acid alkylaminoalkyl ester |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0479889A true JPH0479889A (en) | 1992-03-13 |
Family
ID=16262801
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP19072790A Pending JPH0479889A (en) | 1990-07-20 | 1990-07-20 | Production of acrylic acid or methacrylic acid alkylaminoalkyl ester |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0479889A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005090586A1 (en) * | 2004-03-19 | 2005-09-29 | Ciba Specialty Chemicals Water Treatments Limited | Biocatalytic manufacturing of (meth)acrylylcholine or 2-(n,n-dimethylamino)ethyl (meth)acrylate |
| JP2009517512A (en) * | 2005-11-29 | 2009-04-30 | ビーエーエスエフ ソシエタス・ヨーロピア | Method for transesterification or esterification of side chain in polymer |
| WO2023281077A1 (en) * | 2021-07-09 | 2023-01-12 | Spcm Sa | Method for obtaining a bio-sourced-monomer from renewable dimethylaminoethanol |
-
1990
- 1990-07-20 JP JP19072790A patent/JPH0479889A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005090586A1 (en) * | 2004-03-19 | 2005-09-29 | Ciba Specialty Chemicals Water Treatments Limited | Biocatalytic manufacturing of (meth)acrylylcholine or 2-(n,n-dimethylamino)ethyl (meth)acrylate |
| JP2009517512A (en) * | 2005-11-29 | 2009-04-30 | ビーエーエスエフ ソシエタス・ヨーロピア | Method for transesterification or esterification of side chain in polymer |
| WO2023281077A1 (en) * | 2021-07-09 | 2023-01-12 | Spcm Sa | Method for obtaining a bio-sourced-monomer from renewable dimethylaminoethanol |
| FR3125040A1 (en) * | 2021-07-09 | 2023-01-13 | Snf Sa | Process for obtaining bio-monomer from dimethylaminoethanol of renewable origin |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP0717053B1 (en) | Catalyst for olefin polymerization and process for producing polyolefin using the same | |
| JPS59205991A (en) | Production of butanol by fermentation | |
| JPS61162193A (en) | Production of amide with bacterium | |
| EP0610049A2 (en) | Process for producing optically active alpha-hydroxycarboxylic acid having phenyl group | |
| BG106302A (en) | Hydroxylation of compactin to pravastatin by micromonospora | |
| TWI806890B (en) | Preparation of (meth)acrylates of glycerol carbonate | |
| JPH0479889A (en) | Production of acrylic acid or methacrylic acid alkylaminoalkyl ester | |
| Syldatk et al. | Enantioselective reduction of acetyldimethylphenylsilane by Trigonopsis variabilis (DSM 70714) | |
| KR100592794B1 (en) | Method for preparation of alkyl lactate from lactide using lipase | |
| US5658796A (en) | Optical resolution of alkyl chroman-2-carboxylates | |
| Itoh et al. | Synthesis of enantiomerically pure tributylstannylcyclopropanes through lipase-catalyzed reaction | |
| Kawamoto et al. | Efficient optical resolution of 2-(4-chlorophenoxy) propanoic acid with lipase by the use of organosilicon compounds as substrate: the role of silicon atom in enzymatic recognition | |
| Forró et al. | Preparation of the stereoisomers of 2-cyanocycloalkanols by lipase-catalysed acylation | |
| JP6083431B2 (en) | Method for producing glycerin carbonate acrylate compound | |
| Bel-Rhlid et al. | Microbiological Reduction Ofcarbonyl Groupings: Preparation of Stereoisomers Acyclic Chiral α-Diols | |
| JPH0357752B2 (en) | ||
| JP4405631B2 (en) | Method for purification of conjugated linoleic acid isomers | |
| JPH01132399A (en) | Production of optically active unsaturated alcohol and esterified product thereof | |
| AU655698B2 (en) | Process for producing optically active norborneol | |
| JPH104998A (en) | Production of optically active secondary alcohol | |
| Matsui et al. | Asymmetric oxidation of isopropyl moieties of aliphatic and aromatic hydrocarbons by Rhodococcus sp. 11B | |
| CA2231456A1 (en) | Optical resolution of alkyl 1,4-benzodioxan-2-carboxylates using esterase from serratia marcescens | |
| US5959159A (en) | Method for preparing optically active 5-hydroxy-3-(4'-hydroxyphenyl)-1,1,3-trimethylindane | |
| JP3150813B2 (en) | Process for producing (R) -3-hydroxybutyric acid and its ester | |
| JP2001017193A (en) | Production of monohydroxyadamantane esters |