JPH059185A - Cyclic compound and method for producing the same - Google Patents
Cyclic compound and method for producing the sameInfo
- Publication number
- JPH059185A JPH059185A JP16069691A JP16069691A JPH059185A JP H059185 A JPH059185 A JP H059185A JP 16069691 A JP16069691 A JP 16069691A JP 16069691 A JP16069691 A JP 16069691A JP H059185 A JPH059185 A JP H059185A
- Authority
- JP
- Japan
- Prior art keywords
- formula
- compound
- compound represented
- iii
- same
- 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
- 238000004519 manufacturing process Methods 0.000 title claims description 4
- 150000001923 cyclic compounds Chemical class 0.000 title abstract description 9
- 150000001875 compounds Chemical class 0.000 claims abstract description 29
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- 238000007363 ring formation reaction Methods 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 125000000896 monocarboxylic acid group Chemical group 0.000 claims description 2
- 229920002988 biodegradable polymer Polymers 0.000 abstract description 6
- 239000004621 biodegradable polymer Substances 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 abstract description 4
- 238000000034 method Methods 0.000 abstract description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 13
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 12
- WHBMMWSBFZVSSR-UHFFFAOYSA-N 3-hydroxybutyric acid Chemical compound CC(O)CC(O)=O WHBMMWSBFZVSSR-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- -1 amine compound Chemical class 0.000 description 4
- SYZRZLUNWVNNNV-UHFFFAOYSA-N 2-bromoacetyl chloride Chemical compound ClC(=O)CBr SYZRZLUNWVNNNV-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 229920006158 high molecular weight polymer Polymers 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- AKYXOTBQEFPUEA-UHFFFAOYSA-N 3-(2-bromoacetyl)oxybutanoic acid Chemical compound OC(=O)CC(C)OC(=O)CBr AKYXOTBQEFPUEA-UHFFFAOYSA-N 0.000 description 2
- REKYPYSUBKSCAT-UHFFFAOYSA-N 3-hydroxypentanoic acid Chemical compound CCC(O)CC(O)=O REKYPYSUBKSCAT-UHFFFAOYSA-N 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- RKDVKSZUMVYZHH-UHFFFAOYSA-N 1,4-dioxane-2,5-dione Chemical compound O=C1COC(=O)CO1 RKDVKSZUMVYZHH-UHFFFAOYSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- YAQLSKVCTLCIIE-UHFFFAOYSA-N 2-bromobutyric acid Chemical compound CCC(Br)C(O)=O YAQLSKVCTLCIIE-UHFFFAOYSA-N 0.000 description 1
- KZOBODYIXDMSCF-UHFFFAOYSA-N 2-bromohexanoyl chloride Chemical compound CCCCC(Br)C(Cl)=O KZOBODYIXDMSCF-UHFFFAOYSA-N 0.000 description 1
- OZGMODDEIHYPRY-UHFFFAOYSA-N 2-bromopropanoyl chloride Chemical compound CC(Br)C(Cl)=O OZGMODDEIHYPRY-UHFFFAOYSA-N 0.000 description 1
- HPMGFDVTYHWBAG-UHFFFAOYSA-N 3-hydroxyhexanoic acid Chemical compound CCCC(O)CC(O)=O HPMGFDVTYHWBAG-UHFFFAOYSA-N 0.000 description 1
- NDPLAKGOSZHTPH-UHFFFAOYSA-N 3-hydroxyoctanoic acid Chemical compound CCCCCC(O)CC(O)=O NDPLAKGOSZHTPH-UHFFFAOYSA-N 0.000 description 1
- HPLOUJVSDSYYNU-UHFFFAOYSA-N 7-methyl-1,4-dioxepane-2,5-dione Chemical compound CC1CC(=O)OCC(=O)O1 HPLOUJVSDSYYNU-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VGCXGMAHQTYDJK-UHFFFAOYSA-N Chloroacetyl chloride Chemical compound ClCC(Cl)=O VGCXGMAHQTYDJK-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- YZCKVEUIGOORGS-IGMARMGPSA-N Protium Chemical compound [1H] YZCKVEUIGOORGS-IGMARMGPSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 230000037358 bacterial metabolism Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- JJTUDXZGHPGLLC-UHFFFAOYSA-N lactide Chemical compound CC1OC(=O)C(C)OC1=O JJTUDXZGHPGLLC-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000001766 physiological effect Effects 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- ILWRPSCZWQJDMK-UHFFFAOYSA-N triethylazanium;chloride Chemical compound Cl.CCN(CC)CC ILWRPSCZWQJDMK-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Biological Depolymerization Polymers (AREA)
Abstract
(57)【要約】 （修正有）
【目的】医用高分子及び生分解性高分子の新規原料を提
供する。
【構成】下記式［Ｉ］で表わされる環状化合物及び化合
物［ＩＩ］と化合物［ＩＩＩ］を反応させて式［ＩＶ］
で表される化合物を生成させ、次いでこれを閉環反応さ
せる環状化合物［Ｉ］の製造法
【化１】
(57) [Summary] (Modified) [Purpose] To provide new raw materials for medical and biodegradable polymers. [Structure] A cyclic compound represented by the following formula [I] and a compound [II] are reacted with a compound [III] to form a compound of the formula [IV]
A process for producing a cyclic compound [I], in which a compound represented by
Description
【０００１】[0001]
【産業上の利用分野】本発明は医用高分子及び生分解性
高分子の新規原料及びその製造法に関する。更に本発明
は生理活性を有する新規化合物に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to novel raw materials for medical polymers and biodegradable polymers and a method for producing the same. Furthermore, the present invention relates to novel compounds having physiological activity.
【０００２】[0002]
【従来の技術】最近、地球環境問題のために生分解性ポ
リマーが注目されている。微生物がつくる重合体は、大
地や海洋にすむ微生物によって分解されるので、発酵法
による重合体の製造が検討されている。更に乳酸、グリ
コール酸などを原料とする生分解性ポリマーの合成法も
検討されているが、これらヒドロキシ脂肪族カルボン酸
またはそのエステルを直接重合して高分子量重合体を得
ることはできていない。そのため環状ダイマー、即ちラ
クチド、グリコリド等にして開環重合することにより高
分子量重合体を製造することが検討されている。2. Description of the Related Art Recently, biodegradable polymers have been attracting attention due to global environmental problems. Since polymers produced by microorganisms are decomposed by microorganisms living in the earth or ocean, production of polymers by fermentation has been studied. Furthermore, although a method for synthesizing a biodegradable polymer using lactic acid, glycolic acid or the like as a raw material has been investigated, it has not been possible to directly polymerize these hydroxyaliphatic carboxylic acids or their esters to obtain high molecular weight polymers. Therefore, it has been studied to produce a high molecular weight polymer by ring-opening polymerization of a cyclic dimer, that is, lactide, glycolide or the like.
【０００３】[0003]
【発明が解決しようとする課題】そこで下記構造単位
〔Ｖ〕Therefore, the following structural unit [V]
【０００４】[0004]
【化３】 [Chemical 3]
【０００５】（式〔Ｖ〕中Ｒ1は炭素数１〜１０のアル
キル基を示す。）を有する高分子量重合体はバクテリア
代謝法により、分解されること等を鑑み、式〔Ｉ〕で示
される環状化合物を合成できれば高分子量生分解性ポリ
マーの原料となると考えて鋭意検討を行なった。In view of the fact that a high molecular weight polymer having R 1 in the formula [V] represents an alkyl group having 1 to 10 carbon atoms is decomposed by a bacterial metabolism method, it is represented by the formula [I]. It was thought that it could be a raw material for high molecular weight biodegradable polymer if the cyclic compound can be synthesized.
【０００６】[0006]
【課題を解決するための手段】その結果、下記式〔Ｉ
Ｉ〕で表わされる化合物と下記式〔ＩＩＩ〕で表わされ
る化合物により、下記式〔Ｉ〕で表わされる化合物の合
成に成功し、本発明に到達した。すなわち、本発明の要
旨は下記式〔Ｉ〕As a result, the following formula [I
The compound represented by the formula [I] and the compound represented by the formula [III] have been successfully synthesized to reach the present invention. That is, the gist of the present invention is the following formula [I]:
【０００７】[0007]
【化４】 [Chemical 4]
【０００８】（式〔Ｉ〕中、Ｒ1は炭素数１〜１０のア
ルキル基を示し、Ｒ2は水素原子または炭素数１〜１０
のアルキル基を示す。）で表わされる環状化合物及び下
記式〔ＩＩ〕
ＨＯ−ＣＨＲ1−ＣＨ2ＣＯＯＨ 〔ＩＩ〕
（式〔ＩＩ〕中Ｒ1は式〔Ｉ〕と同じ）で表わされる化
合物と下記式〔ＩＩＩ〕
Ｘ−ＣＨＲ2−ＣＯ−Ｙ〔ＩＩＩ〕
（式〔ＩＩＩ〕中、Ｒ2は式〔Ｉ〕と同じであり、Ｘ、
Ｙはハロゲン原子を示す）で表わされる化合物とを反応
させることにより、下記式〔ＩＶ〕(In the formula [I], R 1 represents an alkyl group having 1 to 10 carbon atoms, and R 2 is a hydrogen atom or 1 to 10 carbon atoms.
Is an alkyl group. ) And a compound represented by the following formula [II] HO-CHR 1 -CH 2 COOH [II] (in the formula [II], R 1 is the same as the formula [I]) and the following formula [III] X —CHR 2 —CO—Y [III] (In the formula [III], R 2 is the same as the formula [I], and X,
Y represents a halogen atom), and a compound represented by the following formula [IV]
【０００９】[0009]
【化５】 [Chemical 5]
【００１０】表わされる化合物を生成させ、次に式〔Ｉ
Ｖ〕で表わされる化合物を閉環反応させることを特徴と
する式〔Ｉ〕で表わされる環状化合物の製造方法に存す
る。以下、本発明を更に詳細に説明する。式〔ＩＩ〕で
表わされる化合物と式〔ＩＩＩ〕で表わされる化合物を
溶媒中に溶解させ、アミン化合物の存在下に反応させる
ことにより、上記式〔ＩＶ〕で表わされる化合物を得、
次に式〔ＩＶ〕で表わされる化合物をアルカリで処理す
ることにより、閉環反応させて式〔Ｉ〕で表わされる本
発明の環状化合物が合成される。A compound of the formula I
V] in the ring-closing reaction of the compound represented by the formula [I]. Hereinafter, the present invention will be described in more detail. A compound represented by the above formula [IV] is obtained by dissolving the compound represented by the formula [II] and the compound represented by the formula [III] in a solvent and reacting them in the presence of an amine compound.
Next, the compound represented by the formula [IV] is treated with an alkali to cause a ring-closing reaction to synthesize the cyclic compound of the present invention represented by the formula [I].
【００１１】本発明で使用される式〔Ｉ〕で表わされる
化合物としては特に限定されるものではないが、具体例
としては、３−ヒドロキシ酪酸、３−ヒドロキシ吉草
酸、３−ヒドロキシカプロン酸、３−ヒドロキシカプリ
ル酸等が挙げられる。特に３−ヒドロキシ酪酸が好まし
い。次に式〔ＩＩＩ〕で表わされる化合物については、
特に限定されるものではないが、ＸはＢｒ、ＹはＣｌで
あるものが特に好ましい。具体例としては、α−ブロモ
アセチルクロリド、α−ブロモプロピオン酸クロリド、
α−クロロアセチルクロリド、α−ブロモ酪酸ブロシ
ド、α−ブロモカプロン酸クロリド、等が挙げられ、特
にα−ブロモアセチルクロリドが好ましい。式〔ＩＩ〕
で表わされる化合物と式〔ＩＩＩ〕で表わされる化合物
の仕込み量比は当量比で１：１０〜１０：１であり、よ
り好ましくは１：２〜２：１である。The compound represented by the formula [I] used in the present invention is not particularly limited, but specific examples include 3-hydroxybutyric acid, 3-hydroxyvaleric acid, 3-hydroxycaproic acid, 3-hydroxycaprylic acid and the like can be mentioned. Particularly, 3-hydroxybutyric acid is preferable. Next, regarding the compound represented by the formula [III],
Although not particularly limited, those in which X is Br and Y is Cl are particularly preferable. As specific examples, α-bromoacetyl chloride, α-bromopropionic acid chloride,
Examples include α-chloroacetyl chloride, α-bromobutyric acid broside, α-bromocaproic acid chloride, and the like, and α-bromoacetyl chloride is particularly preferable. Formula [II]
The equivalent ratio of the amount of the compound represented by the formula (3) to the amount of the compound represented by the formula [III] is 1:10 to 10: 1, and more preferably 1: 2 to 2: 1.
【００１２】式〔ＩＩ〕で表わされる化合物と式〔ＩＩ
Ｉ〕で表わされる化合物を反応させる際の溶媒としては
両化合物を溶解するものであればよく、具体的には、ジ
エチルエーテル、テトラヒドロフラン、ジオキサン、ジ
ブチルエーテル等のエーテル類、トルエン、キシレン、
ｎ−ヘキサンなどの炭化水素類、ジメチルアセトアミ
ド、ジメチルホルムアミド、Ｎ−メチルピロリドン、ア
セトニトリル等が挙げられる。またアミン化合物として
は、トリエチルアミン、トリブチルアミン等の第３級ア
ミン類、ピリジン、キノリン等の芳香族アミン類が使用
でき、特にトリエチルアミンが好ましい。The compound of the formula [II] and the compound of the formula [II
The solvent for reacting the compound represented by the formula [I] may be any solvent capable of dissolving both compounds, and specifically, ethers such as diethyl ether, tetrahydrofuran, dioxane and dibutyl ether, toluene, xylene,
Hydrocarbons such as n-hexane, dimethylacetamide, dimethylformamide, N-methylpyrrolidone, acetonitrile and the like can be mentioned. As the amine compound, tertiary amines such as triethylamine and tributylamine, aromatic amines such as pyridine and quinoline can be used, and triethylamine is particularly preferable.
【００１３】アミンの量は式〔Ｉ〕の化合物と同量以上
５倍程度が好ましい。反応温度は−１０〜１００℃、好
ましくは０〜４０℃であり、反応時間は３０分〜５０時
間、好ましくは５時間〜２０時間である。次に式〔Ｉ
Ｖ〕で表わされる化合物の閉環反応に使用するアルカリ
化合物としては重炭酸ソーダ、炭酸ソーダ、炭酸カリウ
ム、水酸化ナトリウム、水酸化カリウム等が使用でき、
特に重炭酸ソーダが好ましい。本発明の環状化合物は不
剤炭素を含むものであるので、必要に応じて光学活性の
環状化合物とすることもできる。The amount of amine is preferably at least the same amount as the compound of the formula [I] and about 5 times. The reaction temperature is -10 to 100 ° C, preferably 0 to 40 ° C, and the reaction time is 30 minutes to 50 hours, preferably 5 hours to 20 hours. Next, the formula [I
V] can be used as the alkali compound for the ring closure reaction of sodium bicarbonate, sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide and the like.
Sodium bicarbonate is particularly preferable. Since the cyclic compound of the present invention contains non-active carbon, it can be made into an optically active cyclic compound, if necessary.
【００１４】[0014]
【実施例】以下実施例により更に詳細に説明をするがそ
の要旨を越えない限り、この実施例に限定されるもので
はない。
実施例１：３−（α−ブロモアセトキシ）酪酸の合成
３−ヒドロキシ酪酸５ｇ（０．０４８モル）と塩化ブロ
モアセチル（０．０６２モル）をジエチルエーテル１０
０ｍｌに溶解させ、この溶液を氷浴中で攪拌し、５℃以
下に保持しながらトリエチルアミン５．３５ｇ（０．０
５３モル）を含むジエチルエーテル２０ｍｌを３０分間
で滴下した。滴下後室温で１０時間攪拌後、反応溶液か
らトリエチルアミン塩酸塩をろ過して除去し、ろ液を蒸
留水で３回洗浄した。得られたエーテル溶液を硫酸ナト
リウムで脱水した後、エーテルを留去した。その結果淡
黄色の目的の化合物が７０％の収率で得られた。The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples as long as the gist thereof is not exceeded. Example 1 Synthesis of 3- (α-bromoacetoxy) butyric acid 5 g (0.048 mol) of 3-hydroxybutyric acid and bromoacetyl chloride (0.062 mol) were added to diethyl ether 10
Dissolve the solution in 0 ml, stir the solution in an ice bath, and keep 5.35 g (0.0
20 ml of diethyl ether containing 53 mol) was added dropwise over 30 minutes. After the dropping, the mixture was stirred at room temperature for 10 hours, triethylamine hydrochloride was removed from the reaction solution by filtration, and the filtrate was washed 3 times with distilled water. The obtained ether solution was dehydrated with sodium sulfate and then the ether was distilled off. As a result, the pale yellow target compound was obtained in a yield of 70%.
【００１５】実施例２：７−メチル−１，４−ジオキセ
パン−２，５−ジオンの合成
炭酸ナトリウム４ｇ（０．０４８モル）をジメチルホル
ムアミド７５０ｍｌに混合し、室温で激しく攪拌しなが
ら３−（α−ブロモアセトキシ）酪酸７ｇ（０．０３１
モル）を含むジメチルホルムアミド溶液５０ｍｌを１０
時間かけて滴下した。滴下終了後、同温度で２０時間攪
拌を続けた。反応溶液をろ過して不溶の白色沈澱を除去
後、減圧下でジメチルホルムアミドを留去した。残留し
た白濁溶液をアセトンに溶解させ、不溶物のろ別後、ア
セトンを蒸留除去して、生成物を得た。生成物の1Ｈ−
ＮＭＲを図１に示す。Example 2: Synthesis of 7-methyl-1,4-dioxepane-2,5-dione 4 g (0.048 mol) of sodium carbonate was mixed with 750 ml of dimethylformamide, and 3- ( α-Bromoacetoxy) butyric acid 7 g (0.031
50 ml of a dimethylformamide solution containing 10 mol.
It dripped over time. After completion of dropping, stirring was continued at the same temperature for 20 hours. The reaction solution was filtered to remove insoluble white precipitate, and then dimethylformamide was distilled off under reduced pressure. The remaining cloudy solution was dissolved in acetone, the insoluble matter was filtered off, and the acetone was distilled off to obtain a product. 1 H- of product
NMR is shown in FIG.
【００１６】[0016]
【発明の効果】本発明の環状化合物を利用することによ
り容易に医用高分子、生分解性高分子を製造することが
でき、該高分子の工業的生産が可能となった。INDUSTRIAL APPLICABILITY By using the cyclic compound of the present invention, medical polymers and biodegradable polymers can be easily produced, and industrial production of the polymers becomes possible.
【図１】実施例２で得られた環状化合物の1Ｈ−ＮＭＲ
スペクトル図である。FIG. 1 1 H-NMR of the cyclic compound obtained in Example 2.
It is a spectrum figure.
ａ ２．９０ｐｐｍ，シングレット、 ｂ ４．２４ｐｐｍ，マルチプレット ｃ ２．７０ｐｐｍ，マルチプレット ｄ １．２６ｐｐｍ，ダブレット a 2.90 ppm, singlet, b 4.24ppm, multiplet c 2.70 ppm, multiplet d 1.26 ppm, doublet
Claims (2)
し、Ｒ2は水素原子または炭素数１〜１０のアルキル基
を示す。）で表わされる環状化合物1. The following formula [I]: (In the formula [I], R 1 represents an alkyl group having 1 to 10 carbon atoms, and R 2 represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.)
示す。）で表わされる化合物と下記式〔ＩＩＩ〕 Ｘ−ＣＨＲ2−ＣＯ−Ｙ〔ＩＩＩ〕 （式〔ＩＩＩ〕中、Ｒ2は水素原子または炭素数１〜１
０のアルキル基を示し、Ｘ、Ｙはハロゲン原子を示
す。）で表わされる化合物とを反応させることにより下
記式〔ＩＶ〕で表わされる化合物を生成させ、次に式
〔ＩＶ〕で表わされる化合物を閉環反応させることを特
徴とする請求項１の環状化合物の製造法。 【化２】 （式〔ＩＶ〕中、Ｘ、Ｒ1、Ｒ2は式〔ＩＩ〕、〔ＩＩ
Ｉ〕中と同じ）2. A compound represented by the following formula [II] HO-CHR 1 -CH 2 COOH [II] (in the formula [II], R 1 represents an alkyl group having 1 to 10 carbon atoms) and the following formula: during [III] X-CHR 2 -CO-Y (III) (formula (III), R 2 is a hydrogen atom or a carbon atoms 1 to 1
0 represents an alkyl group, and X and Y represent a halogen atom. ) To produce a compound represented by the following formula [IV], and then subject the compound represented by the formula [IV] to a ring-closing reaction. Manufacturing method. [Chemical 2] (In the formula [IV], X, R 1 and R 2 are represented by the formulas [II] and [II
(Same as I)
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16069691A JPH059185A (en) | 1991-07-01 | 1991-07-01 | Cyclic compound and method for producing the same |
| US07/906,675 US5286842A (en) | 1991-07-01 | 1992-06-30 | Process for producing a biodegradable polymer |
| EP19920111071 EP0522422A3 (en) | 1991-07-01 | 1992-06-30 | Process for producing a biodegradable polymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16069691A JPH059185A (en) | 1991-07-01 | 1991-07-01 | Cyclic compound and method for producing the same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH059185A true JPH059185A (en) | 1993-01-19 |
Family
ID=15720495
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP16069691A Pending JPH059185A (en) | 1991-07-01 | 1991-07-01 | Cyclic compound and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH059185A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018119549A1 (en) | 2016-12-26 | 2018-07-05 | 普锐特冶金技术日本有限公司 | Dual-roller continuous casting device |
-
1991
- 1991-07-01 JP JP16069691A patent/JPH059185A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018119549A1 (en) | 2016-12-26 | 2018-07-05 | 普锐特冶金技术日本有限公司 | Dual-roller continuous casting device |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5286842A (en) | Process for producing a biodegradable polymer | |
| RU2674343C2 (en) | 2-oxo-1,3-dioxolane-4-carboxamide building blocks, preparation and use thereof | |
| JPH0723359B2 (en) | Dicyclic stereoisomeric salt of bicyclic imino-α-carboxylic acid ester | |
| HUT54347A (en) | Improved process for producing amidoximes | |
| JPH059185A (en) | Cyclic compound and method for producing the same | |
| JPH023415A (en) | New alpha-oxyacid polymer | |
| CN106543136A (en) | Benzyloxycarbonyl group ethylenediamine trimethylene carbonate and its production and use | |
| SU581860A3 (en) | Method of preparing acyl derivatives of dianhydrohexitols | |
| JPH04112854A (en) | Production of mono-tert-butyl malonate | |
| CN106543153A (en) | 2 imidazoles carbonyl, 2 methyl trimethylene carbonate and its production and use | |
| SU602114A3 (en) | Method of producing n'-(aminoacylaminophenyl)-acetamidines | |
| JPH078853B2 (en) | Method for producing dopamine derivative | |
| SU331541A1 (en) | SHKM LIBRARY | |
| US4232162A (en) | P-Substituted N,N'-bis-(3-oxazolidinyl-2-one)phosphoramides and process for the preparation thereof | |
| DE60004432T2 (en) | Process for the preparation of hydroxamic acids | |
| CN102531929B (en) | A kind of nitrogen-containing, oxygen heteroatom compound and its preparation and application | |
| JPH059272A (en) | Manufacture of polyester | |
| JP2849747B2 (en) | Process for producing oxazolidine-2-ones | |
| CN106554342A (en) | 3,6 dichloromethyl Acetic acid, hydroxy-, bimol. cyclic esters and its production and use | |
| SU416361A1 (en) | METHOD OF OBTAINING ORGAN ORGANIC STRENGTHS AND OIL R-ALKOXYALKEN-A-CARBOXYLIC ACIDS | |
| SU545636A1 (en) | Method of producing aryloxyalkylcarboxylic acid chloroethylamides | |
| SU222372A1 (en) | METHOD FOR PRODUCING N-CARBETOXYMETHYLKARBA- ETHER | |
| SU721425A1 (en) | Method of preparing n,n-disubstituted 2,3,2',3'-tetrahydro-2,2'-diperimidinyls | |
| KR100667678B1 (en) | Method for producing D (-) phenylalanine derivative | |
| CN117945929A (en) | A preparation method of ticagrelor intermediate |