JPH07112974A - (meth)acrylate derivative - Google Patents
(meth)acrylate derivativeInfo
- Publication number
- JPH07112974A JPH07112974A JP5257316A JP25731693A JPH07112974A JP H07112974 A JPH07112974 A JP H07112974A JP 5257316 A JP5257316 A JP 5257316A JP 25731693 A JP25731693 A JP 25731693A JP H07112974 A JPH07112974 A JP H07112974A
- Authority
- JP
- Japan
- Prior art keywords
- meth
- formula
- substances
- group
- compound
- 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
- 150000001252 acrylic acid derivatives Chemical class 0.000 title claims description 15
- 239000000126 substance Substances 0.000 claims abstract description 17
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 4
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims abstract description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 abstract description 15
- -1 oxycarbonylimidazole group Chemical group 0.000 abstract description 13
- 238000006243 chemical reaction Methods 0.000 abstract description 11
- PFKFTWBEEFSNDU-UHFFFAOYSA-N carbonyldiimidazole Chemical compound C1=CN=CN1C(=O)N1C=CN=C1 PFKFTWBEEFSNDU-UHFFFAOYSA-N 0.000 abstract description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 abstract description 6
- 239000003607 modifier Substances 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 5
- 229920001002 functional polymer Polymers 0.000 abstract description 4
- OCNNVWBKEFEIGR-UHFFFAOYSA-N (4-methyl-3-oxopent-4-enyl) imidazole-1-carboxylate Chemical compound CC(=C)C(=O)CCOC(=O)N1C=CN=C1 OCNNVWBKEFEIGR-UHFFFAOYSA-N 0.000 abstract description 3
- 102000004190 Enzymes Human genes 0.000 abstract description 3
- 108090000790 Enzymes Proteins 0.000 abstract description 3
- 102000003886 Glycoproteins Human genes 0.000 abstract description 3
- 108090000288 Glycoproteins Proteins 0.000 abstract description 3
- 239000013543 active substance Substances 0.000 abstract description 3
- 239000000178 monomer Substances 0.000 abstract description 3
- 229920001223 polyethylene glycol Polymers 0.000 abstract description 3
- 125000003396 thiol group Chemical group [H]S* 0.000 abstract description 3
- 239000003814 drug Substances 0.000 abstract description 2
- 229940079593 drug Drugs 0.000 abstract description 2
- 239000000543 intermediate Substances 0.000 abstract description 2
- 150000002632 lipids Chemical class 0.000 abstract description 2
- 239000005445 natural material Substances 0.000 abstract description 2
- 102000004169 proteins and genes Human genes 0.000 abstract description 2
- 108090000623 proteins and genes Proteins 0.000 abstract description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 abstract 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 abstract 1
- 239000003905 agrochemical Substances 0.000 abstract 1
- 150000001720 carbohydrates Chemical class 0.000 abstract 1
- 239000003086 colorant Substances 0.000 abstract 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 15
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 238000005160 1H NMR spectroscopy Methods 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 6
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 5
- 238000000746 purification Methods 0.000 description 5
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000000108 ultra-filtration Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000004566 IR spectroscopy Methods 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 239000003125 aqueous solvent Substances 0.000 description 2
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 238000000502 dialysis Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000001226 reprecipitation Methods 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- ASOKPJOREAFHNY-UHFFFAOYSA-N 1-Hydroxybenzotriazole Chemical compound C1=CC=C2N(O)N=NC2=C1 ASOKPJOREAFHNY-UHFFFAOYSA-N 0.000 description 1
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- NQTADLQHYWFPDB-UHFFFAOYSA-N N-Hydroxysuccinimide Chemical compound ON1C(=O)CCC1=O NQTADLQHYWFPDB-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000001035 drying Methods 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
- 238000000605 extraction Methods 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000002523 gelfiltration Methods 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000012690 ionic polymerization Methods 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000006011 modification reaction Methods 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 125000006353 oxyethylene group Chemical group 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000007870 radical polymerization initiator Substances 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 235000000346 sugar Nutrition 0.000 description 1
- 150000008163 sugars Chemical class 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
- C08F20/10—Esters
- C08F20/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
- C08F20/36—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate containing oxygen in addition to the carboxy oxygen, e.g. 2-N-morpholinoethyl (meth)acrylate or 2-isocyanatoethyl (meth)acrylate
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyethers (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、反応活性な（メタ）ア
クリロイル基およびオキシカルボニルイミダゾール基を
有する（メタ）アクリレート誘導体に関するものであ
る。FIELD OF THE INVENTION The present invention relates to a (meth) acrylate derivative having a reactive (meth) acryloyl group and oxycarbonylimidazole group.
【０００２】[0002]
【従来の技術】（メタ）アクリレート誘導体は重合性に
優れ、比較的合成も容易なことから、機能性高分子の開
発において重要である。そこで機能性物質に簡便に（メ
タ）アクリル基を導入する方法が種々実用化されてお
り、中でもエステル結合あるいはアミド結合による化合
物が多く開発され、実用化されている。しかしこれらの
化合物は、一般に有機溶媒中で８０℃〜１４０℃の高熱
を必要とする脱水縮合あるいはエステル交換反応により
製造されるため、耐熱性の低い化合物に対しては、適応
できるものではなかった。2. Description of the Related Art (Meth) acrylate derivatives are important in the development of functional polymers because they have excellent polymerizability and are relatively easy to synthesize. Therefore, various methods for simply introducing a (meth) acrylic group into a functional substance have been put into practical use, and among them, many compounds having an ester bond or an amide bond have been developed and put into practical use. However, since these compounds are generally produced by dehydration condensation or transesterification reaction requiring high heat of 80 ° C. to 140 ° C. in an organic solvent, they cannot be applied to compounds having low heat resistance. .
【０００３】そこで耐熱性の低い物質に対しては、（メ
タ）アクリル酸クロリドあるいはジシクロヘキシルカル
ボジイミド等の脱水縮合剤を用いる脱水縮合が提案され
ているが、上記脱水縮合剤により活性化エステル基自体
が加水分解を受けやすいため、水中での反応には不向き
であった。また（メタ）アクリル酸を１−ヒドロキシベ
ンゾトリアゾールまたはＮ−ヒドロキシコハク酸イミド
等で活性化エステルとした後、用いる方法もあげられる
が、活性化エステルの製造、精製過程が繁雑である。Therefore, for substances having low heat resistance, dehydration condensation using a dehydration condensation agent such as (meth) acrylic acid chloride or dicyclohexylcarbodiimide has been proposed. Since it is susceptible to hydrolysis, it was unsuitable for reaction in water. A method of using (meth) acrylic acid after making it into an activated ester with 1-hydroxybenzotriazole, N-hydroxysuccinimide or the like can be used, but the production and purification processes of the activated ester are complicated.
【０００４】一方、（メタ）アクリル基をウレタン結合
により機能性物質に導入する試薬として、２−イソシア
ン酸エチルメタクリレートが知られているが、この化合
物はイソシアナート基が空気中の水分により加水分解を
受けやすく、また毒性で刺激性が強く、実用性が低いと
いう問題点がある。On the other hand, 2-isocyanic acid ethyl methacrylate is known as a reagent for introducing a (meth) acryl group into a functional substance through a urethane bond. In this compound, an isocyanate group is hydrolyzed by moisture in the air. It is easily vulnerable, toxic, highly irritating, and low in practicality.
【０００５】[0005]
【発明が解決しようとする課題】本発明の目的は、上記
のような従来の問題点を解決するため、アミノ基、水酸
基、チオール基などの官能基を有する物質中に（メタ）
アクリロイル基を容易に導入でき、また中には水中での
使用も可能な（メタ）アクリレート誘導体を提供するこ
とである。DISCLOSURE OF THE INVENTION The object of the present invention is to solve the above-mentioned problems of the prior art by adding (meta) to a substance having a functional group such as an amino group, a hydroxyl group and a thiol group.
An object of the present invention is to provide a (meth) acrylate derivative which can be easily introduced with an acryloyl group and can be used in water.
【０００６】[0006]
【課題を解決するための手段】本発明者らは、鋭意検討
の結果、反応活性化（メタ）アクリロイル基およびオキ
シカルボニルイミダゾール基の両方を有する（メタ）ア
クリレート誘導体により上記問題点を解決できることを
見い出し、本発明を完成させるにいたった。As a result of intensive studies, the inventors of the present invention have found that the above-mentioned problems can be solved by a (meth) acrylate derivative having both a reaction activated (meth) acryloyl group and an oxycarbonylimidazole group. Found and completed the present invention.
【０００７】すなわち本発明は、下記一般式〔１〕で表
される（メタ）アクリレート誘導体である。That is, the present invention is a (meth) acrylate derivative represented by the following general formula [1].
【化２】 （式中、Ｒは水素原子またはメチル基を示し、ｎはエチ
レンオキシドの平均付加モル数で、１〜２００の正数を
示す。）[Chemical 2] (In the formula, R represents a hydrogen atom or a methyl group, n represents the average number of moles of ethylene oxide added, and represents a positive number from 1 to 200.)
【０００８】本発明において、「（メタ）アクリレー
ト」は「アクリレートおよび／またはメタクリレート」
を意味し、「（メタ）アクリロイル」は「アクリロイル
および／またはメタクリロイル」を意味する。In the present invention, "(meth) acrylate" means "acrylate and / or methacrylate".
And "(meth) acryloyl" means "acryloyl and / or methacryloyl".
【０００９】本発明の（メタ）アクリレート誘導体は前
記一般式〔１〕で表わされる新規かつ有用な化合物であ
り、Ｒおよびｎの違いにより、種々の化合物がこれに含
まれる。これらの（メタ）アクリレート誘導体は（メ
タ）アクリロイル基およびオキシカルボニルイミダゾー
ル基を有する化合物で、ｎが２以上の場合は、オキシエ
チレン鎖の特性が付与されて水溶性が高まり、水系での
利用が可能となる。The (meth) acrylate derivative of the present invention is a novel and useful compound represented by the above general formula [1], and various compounds are included depending on the difference between R and n. These (meth) acrylate derivatives are compounds having a (meth) acryloyl group and an oxycarbonylimidazole group, and when n is 2 or more, the property of the oxyethylene chain is imparted to increase the water solubility and the use in an aqueous system is possible. It will be possible.
【００１０】一般式〔１〕で表わされる本発明の（メ
タ）アクリレート誘導体は、例えば反応式〔２〕に示す
ように、（ポリ）エチレングリコールモノ（メタ）アク
リレートと１，１′−カルボニルジイミダゾールとを反
応させることにより製造することができる。The (meth) acrylate derivative of the present invention represented by the general formula [1] is, for example, as shown in the reaction formula [2], (poly) ethylene glycol mono (meth) acrylate and 1,1'-carbonyldiester. It can be produced by reacting with imidazole.
【化３】 （式中、Ｒおよびｎは前記と同じもの示す。）[Chemical 3] (In the formula, R and n are the same as above.)
【００１１】例えば一般式〔１〕において、Ｒがメチル
基、ｎが１の化合物は、２−ヒドロキシエチルメタクリ
レートと１，１′−カルボニルジイミダゾールとを無溶
媒であるいは有機溶媒中で、−１００〜＋１２０℃、好
ましくは−１０〜＋４０℃で、１分〜１０００時間、好
ましくは１０分〜１２時間反応させることにより製造す
ることができる。For example, in the general formula [1], the compound in which R is a methyl group and n is 1 is a mixture of 2-hydroxyethyl methacrylate and 1,1'-carbonyldiimidazole in the absence of solvent or in an organic solvent. It can be produced by reacting at + 120 ° C, preferably -10 to + 40 ° C for 1 minute to 1000 hours, preferably 10 minutes to 12 hours.
【００１２】上記の反応では、反応系中には水分が存在
しないことが好ましく、よって使用する２−ヒドロキシ
エチルメタクリレート等の原料および有機溶媒は乾燥さ
せたものを用いることが好ましい。また反応に際して
は、乾燥させた窒素、アルゴンなどの不活性ガス雰囲気
下で行うことが好ましい。この際用いられる有機溶媒と
しては、ベンゼン、トルエン、クロロホルム、塩化メチ
レン、テトラヒドロフラン、ジオキサン、アセトニトリ
ルなどがあげられ、またこれらは乾燥させたものを用い
ることが好ましい。In the above reaction, it is preferable that water is not present in the reaction system, and thus it is preferable to use the dried raw materials such as 2-hydroxyethyl methacrylate and the organic solvent. The reaction is preferably carried out in an atmosphere of an inert gas such as dried nitrogen or argon. Examples of the organic solvent used at this time include benzene, toluene, chloroform, methylene chloride, tetrahydrofuran, dioxane, acetonitrile and the like, and it is preferable to use dried ones thereof.
【００１３】反応により生成する（メタ）アクリレート
誘導体は、反応混合物のままで、または単離、精製して
下記用途に用いることができる。単離、精製法として
は、抽出、蒸留、カラム精製、無機剤による吸着精製、
再沈澱、透析、限外ろ過などがあげられる。The (meth) acrylate derivative produced by the reaction can be used as the reaction mixture as it is or after isolation and purification for the following applications. Isolation and purification methods include extraction, distillation, column purification, adsorption purification with inorganic agents,
Examples include reprecipitation, dialysis and ultrafiltration.
【００１４】本発明の（メタ）アクリレート誘導体は、
酵素、抗体、糖蛋白質など生体内外由来の種々の生理活
性物質その他の物質の修飾剤として、また種々の機能性
高分子化合物の原料モノマーなどとして有用である。す
なわち本発明の（メタ）アクリレート誘導体は、オキシ
カルボニルイミダゾール基を有するため、アミノ基、水
酸基、チオール基を有する物質に、比較的穏和な条件下
でウレタン結合、カーボネート結合などを介して（メ
タ）アクリレート基を導入することができ、このため蛋
白質、脂質、糖などの天然物質や、医薬、農薬、色素、
その他の合成物質またはその中間体などの修飾剤として
利用することができる。The (meth) acrylate derivative of the present invention is
It is useful as a modifier for various physiologically active substances such as enzymes, antibodies, and glycoproteins derived from in vivo and other substances, and as a raw material monomer for various functional polymer compounds. That is, since the (meth) acrylate derivative of the present invention has an oxycarbonylimidazole group, it is bonded to a substance having an amino group, a hydroxyl group, and a thiol group via a urethane bond, a carbonate bond, or the like under relatively mild conditions (meth). It is possible to introduce acrylate groups, so natural substances such as proteins, lipids, sugars, drugs, pesticides, pigments,
It can be used as a modifier for other synthetic substances or intermediates thereof.
【００１５】この際の修飾反応は、種々の緩衝液などの
水系溶媒中で、またはジメチルホルムアミド、ジメチル
スルホキシド、ジメチルアセトアミド、ジオキサン、エ
タノール、クロロホルムなどの有機溶媒中で、あるいは
水系溶媒と有機溶媒との混合溶媒中で、−１００〜＋１
２０℃、好ましくは０〜８０℃で、１分〜１０００時
間、好ましくは３０分〜１２時間反応させることにより
行われる。得られた反応物は再結晶、再沈澱、蒸留、透
析、ゲル濾過、限外濾過などにより精製した後、そのま
まで、あるいは凍結乾燥などの処理を経て、機能性物質
として使用される。The modification reaction in this case is carried out in an aqueous solvent such as various buffers or in an organic solvent such as dimethylformamide, dimethylsulfoxide, dimethylacetamide, dioxane, ethanol or chloroform, or in an aqueous solvent and an organic solvent. -100 to +1 in the mixed solvent of
The reaction is carried out at 20 ° C., preferably 0 to 80 ° C., for 1 minute to 1000 hours, preferably 30 minutes to 12 hours. The obtained reaction product is purified by recrystallization, reprecipitation, distillation, dialysis, gel filtration, ultrafiltration, etc., and then used as a functional substance as it is or after undergoing a treatment such as freeze-drying.
【００１６】また本発明の（メタ）アクリレート誘導体
は（メタ）アクリロイル基を有するため、そのままで、
あるいは他の化合物と結合した状態で、単独重合体ある
いは他の共重合可能な化合物との共重合体など高分子の
原料として用いることができる。この際、重合の方法と
しては特に限定されないが、一般に過酸化物、アゾ系化
合物などのラジカル重合開始剤の存在下で、熱、光、レ
ドックスシステムなどによるラジカル重合が可能であ
る。また有機金属化合物や金属アルコラートなどを開始
剤に用いてイオン重合することも可能である。このよう
な重合により分子量１０００から１，０００，０００の
高分子を得ることができる。Since the (meth) acrylate derivative of the present invention has a (meth) acryloyl group,
Alternatively, it can be used as a raw material of a polymer such as a homopolymer or a copolymer with another copolymerizable compound in a state of being bound to another compound. At this time, the method of polymerization is not particularly limited, but in general, radical polymerization by heat, light, redox system or the like can be performed in the presence of a radical polymerization initiator such as a peroxide or an azo compound. It is also possible to carry out ionic polymerization using an organometallic compound or a metal alcoholate as an initiator. By such polymerization, a polymer having a molecular weight of 1,000 to 1,000,000 can be obtained.
【００１７】[0017]
【発明の効果】以上の通り本発明によれば、酵素、抗
体、糖蛋白質などの生理活性物質、その他の物質の修飾
剤、ならびに機能性高分子の原料モノマーなどとして有
用かつ新規な（メタ）アクリレート誘導体が得られる。INDUSTRIAL APPLICABILITY As described above, according to the present invention, it is useful and novel (meta) as a physiologically active substance such as an enzyme, an antibody, a glycoprotein, a modifier for other substances, and a raw material monomer of a functional polymer. An acrylate derivative is obtained.
【００１８】[0018]
【実施例】以下、本発明の実施例について説明するが、
本発明はこれらの実施例に限定されるものではない。 実施例１ 攪拌装置、窒素導入管および温度計を備えた３つ口フラ
スコ中に、モレキュラシーブスで乾燥させた２−ヒドロ
キシエチルメタクリレート１０ｇ（７７ｍｍｏｌ）およ
びベンゼン５０ｍｌを計り取り、これにベンゼン５０ｍ
ｌに１，１′−カルボニルジイミダゾール９．３ｇ（７
７ｍｍｏｌ）を溶解させた溶液を、室温で１時間かけて
滴下し、さらに４時間攪拌した。反応終了後、蒸留水１
００ｍｌで３回洗浄し、有機層を無水硫酸ナトリウムで
乾燥させた後、ベンゼンを減圧下で留去し、無色透明液
体のＮ−（メタクリロイルエチルオキシカルボニル）イ
ミダゾール１７．２ｇ（収率１００％）を得た。EXAMPLES Examples of the present invention will be described below.
The invention is not limited to these examples. Example 1 In a three-necked flask equipped with a stirrer, a nitrogen introduction tube and a thermometer, 10 g (77 mmol) of 2-hydroxyethyl methacrylate dried with molecular sieves and 50 ml of benzene were weighed, and 50 m of benzene was added thereto.
9.3 g (7 g) of 1,1'-carbonyldiimidazole
The solution in which 7 mmol) was dissolved was added dropwise at room temperature over 1 hour and further stirred for 4 hours. After the reaction, distilled water 1
After washing with 00 ml three times and drying the organic layer with anhydrous sodium sulfate, benzene was distilled off under reduced pressure to obtain 17.2 g of N- (methacryloylethyloxycarbonyl) imidazole as a colorless transparent liquid (yield 100%). Got
【００１９】生成物の1Ｈ−ＮＭＲ、ＩＲおよび元素分
析値のデータを以下に示す。なお1Ｈ−ＮＭＲにおける
プロトンの位置を式〔３〕に示す。The data of 1 H-NMR, IR and elemental analysis values of the product are shown below. The position of the proton in 1 H-NMR is shown in formula [3].
【化４】 [Chemical 4]
【００２０】1Ｈ−ＮＭＲ（２７０ＭＨｚ、δ；ｐｐ
ｍ、ＣＤＣｌ3） ８．１４（ｆ、；ｓ、１Ｈ） ７．４３（ｇ、；ｓ、１Ｈ） ７．０８（ｈ、；ｓ、１Ｈ） ６．１４（ｂ、；ｓ、１Ｈ） ５．６２（ａ、；ｓ、１Ｈ） ４．６５（ｅ、；ｔ、２Ｈ、Ｊ＝２．４８） ４．５１（ｄ、；ｔ、２Ｈ、Ｊ＝２．４８） １．９５（ｃ、；ｓ、３Ｈ） 1 H-NMR (270 MHz, δ; pp
m, CDCl 3 ) 8.14 (f,; s, 1H) 7.43 (g,; s, 1H) 7.08 (h,; s, 1H) 6.14 (b,; s, 1H) 5 .62 (a,; s, 1H) 4.65 (e,; t, 2H, J = 2.48) 4.51 (d,; t, 2H, J = 2.48) 1.95 (c, ; S, 3H)
【００２１】ＩＲ（液膜法；ｃｍ-1） １７３０（Ｏ−ＣＯ−ＮＨ） １７２０（ＣＯＯ） １６５２（Ｃ＝Ｃ）IR (liquid film method; cm -1 ) 1730 (O-CO-NH) 1720 (COO) 1652 (C = C)
【００２２】元素分析値（Ｃ10Ｈ12Ｎ2Ｏ4として） 計算値 Ｃ；５３．５５、Ｈ；５．４０、Ｎ；１２．５
０ 実測値 Ｃ；５３．５１、Ｈ；５．４２、Ｎ；１２．４
８Elemental analysis value (as C 10 H 12 N 2 O 4 ) calculated value C; 53.55, H; 5.40, N; 12.5
0 Found C; 53.51, H; 5.42, N; 12.4
8
【００２３】実施例２ 攪拌装置、窒素導入管および温度計を備えた３つ口フラ
スコ中に、モレキュラシーブスで乾燥させたポリエチレ
ングリコールモノメタクリレート（分子量約１５００）
１０ｇ（６．７ｍｍｏｌ）およびジオキサン５０ｍｌを
計り取り、これにジオキサン５０ｍｌに１，１′−カル
ボニルジイミダゾール０．８ｇ（６．７ｍｍｏｌ）を溶
解させた溶液を、室温で１時間かけて滴下し、さらに４
時間攪拌した。反応終了後、減圧下に３０℃でジオキサ
ンを留去し、残渣を蒸留水１００ｍｌに溶解した後、限
外ろ過（分画分子量５００）を繰り返し、最後に凍結乾
燥し、白色粉末状のＮ−（メタクリロイルエチルオキシ
カルボニル）イミダゾールを得た（収率８９％）。Example 2 Polyethylene glycol monomethacrylate (molecular weight about 1500) dried with molecular sieves in a three-necked flask equipped with a stirrer, a nitrogen inlet tube and a thermometer.
10 g (6.7 mmol) and 50 ml of dioxane were weighed, and a solution of 0.8 g (6.7 mmol) of 1,1′-carbonyldiimidazole in 50 ml of dioxane was added dropwise thereto at room temperature over 1 hour, 4 more
Stir for hours. After completion of the reaction, dioxane was distilled off at 30 ° C. under reduced pressure, the residue was dissolved in 100 ml of distilled water, and then ultrafiltration (molecular weight cutoff 500) was repeated, and finally freeze-dried to give N-white powder. (Methacryloylethyloxycarbonyl) imidazole was obtained (yield 89%).
【００２４】生成物の1Ｈ−ＮＭＲおよびＩＲのデータ
を以下に示す。なお1Ｈ−ＮＭＲにおけるプロトンの位
置を式〔４〕に示す。The 1 H-NMR and IR data of the product are shown below. The position of the proton in 1 H-NMR is shown in formula [4].
【化５】 [Chemical 5]
【００２５】1Ｈ−ＮＭＲ（２７０ＭＨｚ、δ；ｐｐ
ｍ、ＣＤＣｌ3） ８．１４（ｊ、；ｓ、１Ｈ） ７．４３（ｋ、；ｓ、１Ｈ） ７．０８（ｍ、；ｓ、１Ｈ） ６．１４（ｂ、；ｓ、１Ｈ） ５．６２（ａ、；ｓ、１Ｈ） ４．７４−４．６５−４．６１（ｉ、；ｍ、２Ｈ） ４．３８−４．２７−４．２３（ｄ、；ｍ、２Ｈ） ３．８１−３．５７（ｅ、ｆ、ｇ、ｈ、；ｍ、１１０
Ｈ） １．９３（ｃ、；ｓ、３Ｈ） 1 H-NMR (270 MHz, δ; pp
m, CDCl 3 ) 8.14 (j,; s, 1H) 7.43 (k,; s, 1H) 7.08 (m,; s, 1H) 6.14 (b,; s, 1H) 5 .62 (a,; s, 1H) 4.74-4.65-4.61 (i,; m, 2H) 4.38-4.27-4.23 (d,; m, 2H) 3. 81-3.57 (e, f, g, h, m, 110
H) 1.93 (c,; s, 3H)
【００２６】ＩＲ（液膜法；ｃｍ-1） １７３０（Ｏ−ＣＯ−ＮＨ） １７２０（ＣＯＯ） １６５２（Ｃ＝Ｃ）IR (liquid film method; cm -1 ) 1730 (O-CO-NH) 1720 (COO) 1652 (C = C)
【００２７】参考例１ 実施例２で得られたＮ−（メタクリロイルエチルオキシ
カルボニル）イミダゾール１ｇおよびベンジルアミン
０．４８ｇをクロロホルム１０ｍｌに溶解させ、還流条
件下で２時間反応させた。室温まで冷却した後、蒸留水
５ｍｌで３回洗浄し、有機層を硫酸ナトリウムで乾燥さ
せた後、減圧下で溶媒を留去し、残渣をベンゼンから再
結晶して、Ｎ−（メタクリロイルエチルオキシカルボニ
ル）アミノベンジルを得た（収率７８％）。Reference Example 1 N- (methacryloylethyloxycarbonyl) imidazole (1 g) obtained in Example 2 and benzylamine (0.48 g) were dissolved in chloroform (10 ml) and reacted under reflux conditions for 2 hours. After cooling to room temperature, it was washed 3 times with 5 ml of distilled water, the organic layer was dried over sodium sulfate, the solvent was distilled off under reduced pressure, and the residue was recrystallized from benzene to give N- (methacryloylethyloxy). Carbonyl) aminobenzyl was obtained (yield 78%).
【００２８】生成物のＩＲのデータを以下に示す。 ＩＲ（ＫＢｒ；ｃｍ-1） １６００、１５８０；フェニル基 １７３２、１６９９；ウレタン結合 １７２０；エステル結合 ８９０；末端ビニル基The IR data of the product is shown below. IR (KBr; cm −1 ) 1600, 1580; Phenyl group 1732, 1699; Urethane bond 1720; Ester bond 890; Terminal vinyl group
Claims (1)
クリレート誘導体。 【化１】 （式中、Ｒは水素原子またはメチル基を示し、ｎはエチ
レンオキシドの平均付加モル数で、１〜２００の正数を
示す。）1. A (meth) acrylate derivative represented by the following general formula [1]. [Chemical 1] (In the formula, R represents a hydrogen atom or a methyl group, n represents the average number of moles of ethylene oxide added, and represents a positive number from 1 to 200.)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5257316A JPH07112974A (en) | 1993-10-14 | 1993-10-14 | (meth)acrylate derivative |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5257316A JPH07112974A (en) | 1993-10-14 | 1993-10-14 | (meth)acrylate derivative |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH07112974A true JPH07112974A (en) | 1995-05-02 |
Family
ID=17304670
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5257316A Pending JPH07112974A (en) | 1993-10-14 | 1993-10-14 | (meth)acrylate derivative |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH07112974A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2024203596A1 (en) * | 2023-03-28 | 2024-10-03 | 日油株式会社 | Method for producing activated polyethylene glycol derivative |
-
1993
- 1993-10-14 JP JP5257316A patent/JPH07112974A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2024203596A1 (en) * | 2023-03-28 | 2024-10-03 | 日油株式会社 | Method for producing activated polyethylene glycol derivative |
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