JPS606649A - Monomer - Google Patents
MonomerInfo
- Publication number
- JPS606649A JPS606649A JP11282483A JP11282483A JPS606649A JP S606649 A JPS606649 A JP S606649A JP 11282483 A JP11282483 A JP 11282483A JP 11282483 A JP11282483 A JP 11282483A JP S606649 A JPS606649 A JP S606649A
- Authority
- JP
- Japan
- Prior art keywords
- enzyme
- compound
- monomer
- acid
- immobilization
- 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.)
- Granted
Links
- 239000000178 monomer Substances 0.000 title claims abstract description 10
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 8
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 claims abstract 2
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 claims description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 abstract description 24
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 abstract description 15
- 102000004190 Enzymes Human genes 0.000 abstract description 11
- 108090000790 Enzymes Proteins 0.000 abstract description 11
- -1 amino compound Chemical class 0.000 abstract description 11
- 229920000642 polymer Polymers 0.000 abstract description 11
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 abstract description 10
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 abstract description 10
- 150000001875 compounds Chemical class 0.000 abstract description 5
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical compound NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 abstract description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 abstract description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 abstract description 2
- 239000013543 active substance 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
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 abstract 1
- 239000000463 material Substances 0.000 abstract 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 150000002148 esters Chemical class 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 150000001408 amides Chemical class 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 229920001519 homopolymer Polymers 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- QIAFMBKCNZACKA-UHFFFAOYSA-N N-benzoylglycine Chemical compound OC(=O)CNC(=O)C1=CC=CC=C1 QIAFMBKCNZACKA-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 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
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 235000001014 amino acid Nutrition 0.000 description 2
- 150000001413 amino acids Chemical class 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- FQOWJGGXNSRNJS-YFKPBYRVSA-N (2s)-2-(2-methylprop-2-enoylamino)propanoic acid Chemical compound OC(=O)[C@H](C)NC(=O)C(C)=C FQOWJGGXNSRNJS-YFKPBYRVSA-N 0.000 description 1
- JMTMSDXUXJISAY-UHFFFAOYSA-N 2H-benzotriazol-4-ol Chemical compound OC1=CC=CC2=C1N=NN2 JMTMSDXUXJISAY-UHFFFAOYSA-N 0.000 description 1
- KAVKUZZRBQNSGV-UHFFFAOYSA-N 4-(2-methylprop-2-enoylamino)benzoic acid Chemical compound CC(=C)C(=O)NC1=CC=C(C(O)=O)C=C1 KAVKUZZRBQNSGV-UHFFFAOYSA-N 0.000 description 1
- ALYNCZNDIQEVRV-UHFFFAOYSA-M 4-aminobenzoate Chemical compound NC1=CC=C(C([O-])=O)C=C1 ALYNCZNDIQEVRV-UHFFFAOYSA-M 0.000 description 1
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 101150065749 Churc1 gene Proteins 0.000 description 1
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 1
- QNAYBMKLOCPYGJ-REOHCLBHSA-N L-alanine Chemical compound C[C@H](N)C(O)=O QNAYBMKLOCPYGJ-REOHCLBHSA-N 0.000 description 1
- NQTADLQHYWFPDB-UHFFFAOYSA-N N-Hydroxysuccinimide Chemical compound ON1C(=O)CCC1=O NQTADLQHYWFPDB-UHFFFAOYSA-N 0.000 description 1
- 102100038239 Protein Churchill Human genes 0.000 description 1
- GJIHEUWBNOBNCM-UHFFFAOYSA-N [BrH]1C=CC=C1 Chemical compound [BrH]1C=CC=C1 GJIHEUWBNOBNCM-UHFFFAOYSA-N 0.000 description 1
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 description 1
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 1
- 235000004279 alanine Nutrition 0.000 description 1
- 238000005267 amalgamation Methods 0.000 description 1
- BLFLLBZGZJTVJG-UHFFFAOYSA-N benzocaine Chemical compound CCOC(=O)C1=CC=C(N)C=C1 BLFLLBZGZJTVJG-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 125000005678 ethenylene group Chemical group [H]C([*:1])=C([H])[*:2] 0.000 description 1
- PQJJJMRNHATNKG-UHFFFAOYSA-N ethyl bromoacetate Chemical compound CCOC(=O)CBr PQJJJMRNHATNKG-UHFFFAOYSA-N 0.000 description 1
- 229960003750 ethyl chloride Drugs 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- NPZTUJOABDZTLV-UHFFFAOYSA-N hydroxybenzotriazole Substances O=C1C=CC=C2NNN=C12 NPZTUJOABDZTLV-UHFFFAOYSA-N 0.000 description 1
- 230000003100 immobilizing effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- DCUFMVPCXCSVNP-UHFFFAOYSA-N methacrylic anhydride Chemical compound CC(=C)C(=O)OC(=O)C(C)=C DCUFMVPCXCSVNP-UHFFFAOYSA-N 0.000 description 1
- VHRYZQNGTZXDNX-UHFFFAOYSA-N methacryloyl chloride Chemical compound CC(=C)C(Cl)=O VHRYZQNGTZXDNX-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 235000018102 proteins Nutrition 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 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
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
この発明は新規なモノマーに関するものである。本発明
の物質を用いて得られる重合体は、アミン化合物と置換
しやすい側鎖を持つており、これを利用して酵素固定や
医薬分野での利用が期待できる。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) This invention relates to a novel monomer. The polymer obtained using the substance of the present invention has a side chain that is easily substituted with an amine compound, and can be expected to be used for enzyme immobilization and in the pharmaceutical field.
：従来技術）
酵素固定化用担体は、一般捉酵素のアミノ基と容易に反
応する官能基を含む必要がある。(Prior art) An enzyme immobilization carrier needs to contain a functional group that easily reacts with the amino group of a general captured enzyme.
εの分野でＰ−メタクリルアミド安息香酸のある種のエ
ステル及びそれからつ（られたポリマーが知られており
、酵素のアミン基と反応してエステルを構成していたヒ
ドロキシル化合物（ヒドロキシベンゾトリアゾールやＮ
−ヒドロキシコハク酸イミド）が離れ、代って酵素がア
ミドの形でポリマー側鎖に固定される活性をもつことが
知られている。（ＬｕＣｈｅｎ Ｇｘｕｎ等、Ｊ、Ｐｏ
ｌｙｍ、 Ｓｅｔ、、 Ｃｈｅｍ、 Ｅｄ、。Certain esters of P-methacrylamidobenzoic acid and polymers derived therefrom are known in the field of ε, and hydroxyl compounds (such as hydroxybenzotriazole and N
-Hydroxysuccinimide) is released, and the enzyme is known to have an activity in which the enzyme is fixed to the polymer side chain in the form of an amide. (LuChen Gxun et al., J. Po
lym, Set, Chem, Ed.
ｒｑ、３３３３＜＋ｑｇ＋’＞）Ｌかし、この化合物は
ヒドロキシル化合物成分としてきわめて特殊な原料を用
いている。rq, 3333<+qg+'>) This compound uses very special raw materials as the hydroxyl compound component.
一方、メタクリル酸のエトキシカルボニルメチルエステ
ルも公知であるが、ポリマー中に入れて上記のようなア
ミノ化合物との反応活性をもたせ得るのは共重合体とし
てわずかな割合で用いた場合のみである。（Ｈ，に６ｓ
ｔｅｒ等、Ａｎｇｅｗ、Ｃｈｅｍ、、ｓｓ、５７６（１
９７６）； 同。On the other hand, ethoxycarbonyl methyl ester of methacrylic acid is also known, but it can be incorporated into a polymer to provide reaction activity with the above-mentioned amino compound only when used in a small proportion as a copolymer. (H, 6s
ter et al., Angew, Chem,, ss, 576 (1
976); Same.
Ｍａｋｒｏｍｏｌ、Ｃｈｅｍ、、１８１．２４９５＜１
９８０＞ ）（発明の目的）
本発明は、酵素、蛋白質、薬理活性物質などのアミノ化
合物と反応してこれを固定化するはたらきをもつ物質を
特徴とする特に合成が容易で、活性な側鎖を持った高分
子量のホモポリマーを形成する能力をもつモノマーを提
供するものである。Makromol, Chem, 181.2495<1
980>) (Object of the Invention) The present invention is characterized by a substance that has the function of reacting with and immobilizing amino compounds such as enzymes, proteins, and pharmacologically active substances, which is particularly easy to synthesize and has an active side chain. The present invention provides a monomer capable of forming a high molecular weight homopolymer having the following properties.
（発明の構成）
この発明は、一般式
％式％
で表わされるモノマーである。こ＼でＡ、 ＢはＮＨ−
Ｙ−Ｃｏで表わされるアミノカルボン酸にもとづく２価
の基、又は０ＣＨｚＣＯで表わされろグリコール酸にも
とづく２価の基であって一１ＡとＢとは異なるものであ
る。またＲは水素原子又はメチル基である。またＲ′は
エチル、ブチル、メチルなどの低級アルキル基であり、
Ｙはメチレン、エチリデン、エチレン、トリメチレン、
テトラメチレン又＆ｉＰ−フェニレンなど２価の炭化水
素基である。(Structure of the Invention) This invention is a monomer represented by the general formula %. This is A, B is NH-
A divalent group based on aminocarboxylic acid represented by Y-Co, or a divalent group based on glycolic acid represented by 0CHZCO, which is different from 1A and B. Moreover, R is a hydrogen atom or a methyl group. Further, R' is a lower alkyl group such as ethyl, butyl, methyl,
Y is methylene, ethylidene, ethylene, trimethylene,
It is a divalent hydrocarbon group such as tetramethylene or &iP-phenylene.
即ち、この化合物のうち、Ａ＝ＮＨ−Ｙ−ＣＯのものは
重合性成分としてのアクリロイル（Ｒ＝Ｈの場合）又は
メタクツロイル（Ｒ’ ＝ＣＨ３）部分にアミド結合で
迷ったアミノカルボン酸成分を介して、ゲルコール酸エ
ステル成分力１そのヒドロキシ基のエステルとして結合
した構成をもっている。また、Ａ ” ＯＣＨ２ＣＯで
あるものはアクリル−グリコール酸−アミノ酸の順番で
連った構造をもつアクリルエステルであり、いずれの場
合も重合性の化合物（モノブー）である。That is, among these compounds, those in which A = NH-Y-CO have an aminocarboxylic acid component lost in an amide bond in the acryloyl (in the case of R = H) or methacturoyl (R' = CH3) moiety as a polymerizable component. The gelcolic acid ester component has a structure in which its hydroxyl group is bonded as an ester. Further, A '' OCH2CO is an acrylic ester having a structure in which acrylic acid-glycolic acid-amino acid are linked in the order, and in either case, it is a polymerizable compound (monobu).
本発明のモノマーをＲ’＝ＣｚＨｓ、Ｙ＝ＣｅＨ＜及び
Ｙ ＝ ＣＨＣＨｓの場合につ℃・て列挙すると次の通
りである。The monomers of the present invention are listed below in °C when R'=CzHs, Y=CeH< and Y=CHCHs.
Ｃ）ｈ ＝ＣＲＣＯＮＨＣｓ Ｈ４ＣＯＯＣＨ２ＣＯＯ
Ｃ２Ｈ５（１）ＣＨ３
ＣＨ２＝ＣＲＣＯＯＣＩ４２ Ｃ０ＮＨＣｓ Ｈ４ＣＯ
ＯＣ２Ｈｓ （３）ＣＨ２＝ＣＲＣＯＯＣＨ２ＣＯＮＨ
ＣＨＣＯＯＣ２Ｈ６（４）占Ｈ３〜
（作用、効果）
本発す」のモノマーは公知の手法で重合させることによ
り、特徴ある構造の側鎖を持ったホモポリマー又はコポ
リマーとすることができる。この側鎖にはグリコール酸
エステルのヒドロキシル基がアミノカルボン酸のカルボ
キシル基と縮合したエステル結合を持っており、このよ
うなアミノ酸−グリコール酸の間のエステルは、酵素な
どのアミノ化合物によって置換される活性がすぐれてい
ると期待できる。このような反応性は低分子化合物にお
いては馬尿酸−グリコール酸の間のエステルについて知
られていたが（ＲｌＳｃｈｗｙｚｅｒ等、Ｈｅ１ｖ Ｃ
ｈｉｍ、 Ａｃｔａ、 ３８．６９（１９５５） ）、
ポリマーの側鎖にこの結合を導入し、酵素固定などに応
用することは新規な技術思想である。C) h = CRCONHCs H4COOCH2COO
C2H5(1)CH3 CH2=CRCOOCI42 C0NHCs H4CO
OC2Hs (3) CH2=CRCOOCH2CONH
CHCOOC2H6(4)Use H3~ (Function, Effect) By polymerizing the monomer of the present invention by a known method, it can be made into a homopolymer or copolymer having a side chain with a characteristic structure. This side chain has an ester bond in which the hydroxyl group of the glycolic acid ester is condensed with the carboxyl group of the aminocarboxylic acid, and this ester between an amino acid and glycolic acid can be substituted by an amino compound such as an enzyme. It can be expected to have excellent activity. Such reactivity was known for esters between hippuric acid and glycolic acid in low molecular weight compounds (RlSchwyzer et al., He1v C
Him, Acta, 38.69 (1955)),
Introducing this bond into the side chain of a polymer and applying it to enzyme immobilization is a novel technical idea.
・ ゴ
また前記ＫＯ８ｔｅｒ等の文献のものと異なり、アク１
ノル構成分とグリコール酸エステル成分との間にアミノ
酸成分を介しているこの型のモノマーは、ホモポリマー
なと、活性基を高頻度に含む形で利用することができる
。・ Unlike the literature of KO8ter and others mentioned above, Aku1
This type of monomer, in which an amino acid component is interposed between the nor component and the glycolic acid ester component, can be used in the form of a homopolymer, which frequently contains active groups.
以下具体例により本発明を説明する。The present invention will be explained below using specific examples.
例１゜
ｐ−アミノ安息香酸エチルをトリエチルアミンの存在下
フ。Example 1 Ethyl p-aminobenzoate was dissolved in the presence of triethylamine.
ロモ酢酸プロミドと反応させアミノ基のブロモアセチル
化物ＢｒｃＨ，ｃｏＮｎｃ、ｕ４ｃｏｏｃ！ＩＨ，（１
）を得た。Bromoacetylated amino group BrcH, coNnc, u4cooc! IH, (1
) was obtained.
ｍ、ｐ １２２．５−１２４．５℃（ｌ ｉｔ 、 １
２１．０−１２１．５℃）以下余白
１（、Ｗ、Ｊｏｈｒｓｏｎ Ｊｒ、、ａｎｄ Ｙ、Ｉｗ
ａｔａ’、Ｊ、Ｏｒｇ。m, p 122.5-124.5°C (l it, 1
21.0-121.5℃) or less margin 1 (, W, Johnson Jr., and Y, Iw
ata', J, Org.
Ｃｈｅｍ ３Ｇ、 １９２１（１９７１ン０．０７２モ
ルのアクリル酸又はメタクリルｍと０．０６モルの工を
少Ｉｆのハイドロキノンを含む１８０ゴの酢酸エチル中
、０．０７２モルのトリエチルアミン存在下で４時間歳
流する０故冷稜、反応混合物を水に注ぎ、酢エチ層を分
離、水層を酢エチで一度抽出し、有機１９＃と抽出液の
混合物を飽和炭酸水系ナトリウム水溶液で一度、純水で
二度洗浄後、硫酸ナトリウムで脱水し、酢エチを減圧下
で除去し、残渣をハイドロキノンを含む溶媒で二度再結
晶する。Chem 3G. Pour the reaction mixture into water, separate the ethyl acetate layer, extract the aqueous layer once with ethyl acetate, and mix the mixture of organic 19# and extract with a saturated aqueous sodium carbonate solution once and with pure water. After washing twice, it is dried over sodium sulfate, the ethyl acetate is removed under reduced pressure, and the residue is recrystallized twice from a solvent containing hydroquinone.
（３，Ｒ＝Ｈ） 収率５９．３％、ｍｐ、６９．５〜７
０．５℃（ベンゼン：ヘキサン＝２：１）
ｆｏｕｎｄ Ｃ：６０．９０． Ｈ：５．６１． Ｎ：
４．９１ｃａｌｅｄ ｃ：ｃｔｏ、ｅｓ、Ｈ：５．４１
． Ｎ：５．０５Ｈｓ
収率６６． Ｉ Ｘ 、 ｍｐ−９５，０〜９５．５℃
（ベンゼンから） （ａ、 Ｒ＝ＣＨｓ ）
ｆｏｕｎｄ Ｃ：６１．９２１ ｆｉ：５．ｓｏ、Ｎ：
４．８１ｃａｌｃｄ Ｃ：６１．８６． Ｈ：５．８４
． Ｎ：４．８２例 ２．（重合方法）
モノ−ｒ −１あるいはＩｌｌ １． ｏ ｇを１０ｄ
ノＤｆｖＩＩｉ″に浴解し、５．６＋ｙのアゾビスイソ
ブチロニトリルを開始剤として加える。反応溶液を重合
管に入れ、爪金管’＆窒素パージして溶封する。６０℃
の恒温槽で４０〜６５時間靜置重合装る。(3, R=H) Yield 59.3%, mp, 69.5-7
0.5°C (benzene:hexane=2:1) Found C: 60.90. H:5.61. N:
4.91caled c:cto,es,H:5.41
．． N: 5.05Hs Yield 66. IX, mp-95,0-95.5℃
(from benzene) (a, R=CHs) found C:61.921 fi:5. so, N:
4.81calcd C:61.86. H:5.84
．． N: 4.82 cases 2. (Polymerization method) Mono-r-1 or Ill 1. o g to 10d
Add 5.6+y of azobisisobutyronitrile as an initiator.Pour the reaction solution into a polymerization tube, purge with nitrogen and melt seal at 60°C.
Polymerization was carried out in a constant temperature bath for 40 to 65 hours.
菫合併液を水中に注いで析出するポリマーをｒ別、乾燥
する。粘度は０．５９７ でＤＭＦ中３０℃で測定
■から、収率８０％前後で還元粘度０．０７〜０．０９
のポリマーを
ＩＩＩから、収第８０％前後で還元粘度０．２２〜０．
２５のポリマーをそれぞれ得た。The violet amalgamation solution is poured into water, and the precipitated polymer is separated and dried. The viscosity is 0.597, measured at 30℃ in DMF.
Polymer from III, with a reduced viscosity of 0.22 to 0.5% at around 80% yield.
25 polymers were obtained.
いづれのポリマーもアセトン、ＤＩＶＩＦＳＤＭＳＯに
”Ｔ ｇｉ 。Both polymers were mixed with acetone and DIVIF SDMSO.
例 ３゜
（１１１％ルのｐ−アミノ安息香ばと１モルのブロモｌ
！ｔＷエチルと１モルのトリエチルアミンとをｏ＋：酸
エテル６００Ｑに加え、混合物を６時間速流する◎放冷
後反応混合物を水に注ぎ、岬エチ７ｍを分離、水層を匪
エテで一度抽出し、翁截層と酢エテ層を合せて純水で二
度抗浄し、硫酸ナトリウムで脱水後部エチを減圧様縮す
る０残渣な放置すると
（Ｖ）が結晶として析出するので１別し、ｆ液に石油エ
ーテルを加えて一晩冷蔵犀に放置。Example 3゜(111% l p-aminobenzoate and 1 mole bromo l)
! Add tW ethyl and 1 mol of triethylamine to o+:acid ether 600Q, and flow the mixture rapidly for 6 hours ◎ After cooling, pour the reaction mixture into water, separate Misaki Ethi 7m, and extract the aqueous layer once with Io Ether. , Combine the Okinagi layer and the acetic acid layer, anti-purify twice with pure water, dehydrate with sodium sulfate, and then condense the ethyl chloride under reduced pressure. If the residue is left to stand, (V) will precipitate as crystals, so separate it. Add petroleum ether to the liquid and leave it in the refrigerator overnight.
析出してくる
１ｖは温ベンゼンに溶解し、石油エーテルを加えて再結
晶。■はメタノールから１与結晶する。The precipitated 1v was dissolved in warm benzene and recrystallized by adding petroleum ether. (2) is crystallized from methanol.
１ｖのｆｏｕｎｄ Ｃ：５８Ｂ３． Ｈ：５．８７．
Ｎ：６．３２Ｖのｆｏｕｎｄ Ｃ：５８．５１． ）Ｇ
５．７７、Ｎ：６．２２１ｖと■υｃａｌｃｄ Ｃ：５
９．１９． ｌ（：５．８２． Ｎ：６．２９＋２１０
．０１モルのＩＶ、アクリル敵クロリド０．０１モル、
０．０１モルのトリエチルアミント？Ｊ＞最のハイドロ
キノンを含む４０ｄの酢酸エチルに加え、反応混合物を
６時間呈温で催拌する０反応混合物を水で−ｒＭｌ、飽
和戻藏水緊ナトリウム水浴敢で一度、純水で二匪ｖ“【
１浄後、懺畝ナトリウムで脱水後、ｏｒ−改エチルを減
圧除去し、９！４渣を少量のハイドロキノンな含むベン
ゼンから再結晶する。収コイ６４９．１％。1v found C:58B3. H:5.87.
N: 6.32V found C: 58.51. )G
5.77, N: 6.221v and ■υcalcd C: 5
9.19. l(:5.82.N:6.29+210
．． 01 mole IV, 0.01 mole of acrylic chloride,
0.01 mole of triethylamine? Add 40 d of ethyl acetate containing the first hydroquinone and stir the reaction mixture at room temperature for 6 hours. Reconstitute the reaction mixture with water - rMl, resaturate once in a sodium water bath and twice with pure water. v “[
After 1 purification and dehydration with Naoden sodium, the or-modified ethyl was removed under reduced pressure, and the 9!4 residue was recrystallized from benzene containing a small amount of hydroquinone. Yield: 649.1%.
Ｉｍｐ、 １２５〜１２６℃。Imp, 125-126°C.
＝（１、Ｒ＝）ｉ）
Ｖｌ ｆｏｕｎｄ Ｃ：６０．６１． Ｈ：５．４８．
Ｎ：４．９１ｃａｌｃｄ Ｃ：６０．６５． ［：５
．４２＋ Ｎ：５．０５例 ４
００３モルのＩＶと無水メタクリル酸０．０４モルとを
１５０ｍｌの酢エチ中に加え、６時間室温で攪拌する。=(1,R=)i) Vl found C:60.61. H:5.48.
N: 4.91 calcd C: 60.65. [:5
．． 42+ N: 5.05 Example 4 003 mol of IV and 0.04 mol of methacrylic anhydride are added to 150 ml of ethyl acetate and stirred for 6 hours at room temperature.
混合物を飽和炭酸水溶液で一度、純水で二度洗浄後、硫
酸す） ＩＪウムで脱水後、酢酸エチルを減圧下に除去
。残渣をハイドロキノンの少量を含むベンゼンから再結
晶した。The mixture was washed once with a saturated aqueous carbonate solution and twice with pure water, then dried over sulfuric acid (IJ), and ethyl acetate was removed under reduced pressure. The residue was recrystallized from benzene containing a small amount of hydroquinone.
収率８１３％。ｍｐ、８７〜８８℃（■） −（ｉ 、
Ｒ＝ＣＨ３）ｖｎ ｆｏｕｎｄ Ｃ：６１．３１．、
Ｈ：５．９１． Ｎ：４．８１ｃａｌｃｄ Ｃ：６１
．８５１ Ｈ：５．８４１ Ｎ：４．８１例 ５
■あるいは■を１．Ｏｇとり、ＤＭＦあるいはＤＭＳｏ
ｌｏｍｌに溶解し、１モル％のＡＩＢＮを開始剤として
封管中、６０℃で４０時間重合した。Ｍ合溶液を水に注
ぎ、沈澱するポリマーを１別して乾燥する。Yield 813%. mp, 87-88℃ (■) −(i,
R=CH3)vn found C:61.31. ,
H:5.91. N: 4.81 calcd C: 61
．． 851 H: 5.841 N: 4.81 Example 5 ■ or ■ 1. Og, DMF or DMSo
1 mol % of AIBN as an initiator and polymerized at 60° C. for 40 hours in a sealed tube. The M mixture solution is poured into water, and the precipitated polymer is separated and dried.
溶媒 収 率 還元粘度 ■から ＤＭＦ ６８．３ ０．１９ ＤＭ５０ ８１．３ ０．６５ ■から ＤＭＦ ７４．９ ０．２１ ＤＭ５０ ７３．７ ０．３８ 還元粘度は、Ｏ，”４／ 、ＤＭＦ中３０℃で測定。Solvent yield reduced viscosity ■From DMF 68.3 0.19 DM50 81.3 0.65 ■From DMF 74.9 0.21 DM50 73.7 0.38 Reduced viscosity was measured at 30° C. in DMF, O,”4/ .
例 ６
メタクリル酸クロリドとアラニンとからジョンテン・バ
ウマン法でＮ−メタクリロイルアラニンを得、これをブ
ロモ酢酸エチルとトリエチルアミンの存在下縮合させて
Ｎ−メタクリロイルアラニンエトキシカルボニルメチル
エステル（■）＝（２，Ｒ＝ＣＨ３）を得た。反応は酢
酸エチル溶媒を用い、６時間加熱還流させておこなった
。収率９４７％。Example 6 N-methacryloylalanine was obtained from methacrylic acid chloride and alanine by the Jonten-Bauman method, and this was condensed with ethyl bromoacetate in the presence of triethylamine to obtain N-methacryloylalanine ethoxycarbonylmethyl ester (■) = (2, R =CH3) was obtained. The reaction was carried out using ethyl acetate as a solvent and heated under reflux for 6 hours. Yield 947%.
ｆｏｕｎｄ Ｃ：５４．７６、 Ｈニア、２０． Ｎ：
５．７１ｃａｌｅｄ Ｃ：５４．３１． Ｈニア、００
． Ｎ：５．７６（■）の重合は、例５と同様にＤＭＦ
中でおこない、還元粘度０．１２の重合物を６６９％収
率でた０
なお、（■）〜（Ｖｌｌｌ）のスペクトルの所見は下記
の通りである。Found C: 54.76, H near, 20. N:
5.71caled C:54.31. H near, 00
．． Polymerization of N: 5.76 (■) was carried out using DMF as in Example 5.
In addition, the findings of the spectra of (■) to (Vllll) are as follows.
（Ｖｌ）はＩＲスペクトルで１６５０ｃｍ にアミド、
１７１０．１７４０ ｃｎＬ−１にエステルの吸収、Ｎ
ＭＲスペクトルテハ９：５〜８．ＯＦにフェニルプロト
ンＢ５１１ｐ［ｎにアミドのプロトン、６．２．６．４
−にビニル基についたメチレン、４８Ｐにメチレンプロ
トン、１，５．１．２ｐｐＨｌにメチルプロトンのピー
クを有し、（ＶＩＤはＩＲスペクトルで（ＶＤと同様で
あるが、ＮＭＲスペクトルでは７．７Ｆにフェニルプロ
トン、５７．５．３ Ｆに（ＣＨ２＝）ンのピークが現
れた。（■）のＩＲスペクトルは１６０ ｏｃＴＬ−ｔ
に二重結合の吸収、ＮＭＲスペクトルでは７．９．８．
１−にアミドプロトン、５６．５、２ ｐｐＨｌに（Ｃ
Ｈ２＝）のプロトンのピークが現れた０
特許出願人
ダイセル化学工業株式会社(Vl) is an amide at 1650 cm in the IR spectrum,
1710.1740 Absorption of ester in cnL-1, N
MR Spectrum Teha 9:5-8. Phenyl proton B511p in OF [amide proton in n, 6.2.6.4
- has methylene attached to the vinyl group, methylene proton at 48P, methyl proton peak at 1,5.1.2ppHl, (VID is IR spectrum (same as VD, but NMR spectrum is 7.7 A peak of (CH2=)ton appeared at phenyl proton, 57.5.3 F. The IR spectrum of (■) was 160 ocTL-t
The absorption of the double bond is 7.9.8 in the NMR spectrum.
Amide proton at 1-, 56.5, 2 ppHl (C
H2=) proton peak appeared 0 Patent applicant Daicel Chemical Industries, Ltd.
Claims (1)
水素原子又はメチル基であり、ＡＮＢはＮＨ−Ｙ−ＣＯ
で表わされるアミノカルボン酸成分又は０ＣＨＣＯで表
わされるグリコール酸成分であり、ＡとＢは異なるもの
である。 Ｙは２価の炭化水素残基な、Ｒ′は低級アルキル基を意
味する。） で表わされるモノマー。[Claims] In the general formula CH2=CRCOABOR', R is a hydrogen atom or a methyl group, and ANB is NH-Y-CO
A and B are different. Y is a divalent hydrocarbon residue, and R' is a lower alkyl group. ) A monomer represented by
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11282483A JPS606649A (en) | 1983-06-24 | 1983-06-24 | Monomer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11282483A JPS606649A (en) | 1983-06-24 | 1983-06-24 | Monomer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS606649A true JPS606649A (en) | 1985-01-14 |
| JPH0429660B2 JPH0429660B2 (en) | 1992-05-19 |
Family
ID=14596448
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11282483A Granted JPS606649A (en) | 1983-06-24 | 1983-06-24 | Monomer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS606649A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010222361A (en) * | 1995-08-11 | 2010-10-07 | Bayer Animal Health Gmbh | Didepsipeptide and application the same as endoparasiticidal agent |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS55160746A (en) * | 1979-05-29 | 1980-12-13 | American Cyanamid Co | Activated ester monomer and polymer |
| JPS56166212A (en) * | 1980-03-14 | 1981-12-21 | Polaroid Corp | Novel polymer and photographic product containing it |
-
1983
- 1983-06-24 JP JP11282483A patent/JPS606649A/en active Granted
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS55160746A (en) * | 1979-05-29 | 1980-12-13 | American Cyanamid Co | Activated ester monomer and polymer |
| JPS56166212A (en) * | 1980-03-14 | 1981-12-21 | Polaroid Corp | Novel polymer and photographic product containing it |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010222361A (en) * | 1995-08-11 | 2010-10-07 | Bayer Animal Health Gmbh | Didepsipeptide and application the same as endoparasiticidal agent |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0429660B2 (en) | 1992-05-19 |
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