JPH04312582A - New 1,3-dioxolane compound - Google Patents
New 1,3-dioxolane compoundInfo
- Publication number
- JPH04312582A JPH04312582A JP3162000A JP16200091A JPH04312582A JP H04312582 A JPH04312582 A JP H04312582A JP 3162000 A JP3162000 A JP 3162000A JP 16200091 A JP16200091 A JP 16200091A JP H04312582 A JPH04312582 A JP H04312582A
- Authority
- JP
- Japan
- Prior art keywords
- compound
- methyl
- dioxolane
- formula
- polyacetal
- 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 1,3-dioxolane compound Chemical class 0.000 title abstract description 21
- 239000000126 substance Substances 0.000 claims description 8
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical class C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 claims description 3
- 229920006324 polyoxymethylene Polymers 0.000 abstract description 17
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 abstract description 15
- 150000001875 compounds Chemical class 0.000 abstract description 12
- 239000003054 catalyst Substances 0.000 abstract description 9
- BGJSXRVXTHVRSN-UHFFFAOYSA-N 1,3,5-trioxane Chemical compound C1OCOCO1 BGJSXRVXTHVRSN-UHFFFAOYSA-N 0.000 abstract description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 abstract description 4
- 230000002378 acidificating effect Effects 0.000 abstract description 4
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical compound OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 abstract description 3
- 125000000217 alkyl group Chemical group 0.000 abstract description 3
- 150000001728 carbonyl compounds Chemical class 0.000 abstract description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 abstract description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 abstract 3
- 239000004215 Carbon black (E152) Substances 0.000 abstract 1
- 229930195733 hydrocarbon Natural products 0.000 abstract 1
- 150000002430 hydrocarbons Chemical class 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 16
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 15
- 239000002904 solvent Substances 0.000 description 14
- 229930182556 Polyacetal Natural products 0.000 description 13
- 238000000034 method Methods 0.000 description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 9
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 9
- 238000002329 infrared spectrum Methods 0.000 description 8
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000009835 boiling Methods 0.000 description 6
- 238000001819 mass spectrum Methods 0.000 description 6
- WXUAQHNMJWJLTG-VKHMYHEASA-N (S)-methylsuccinic acid Chemical compound OC(=O)[C@@H](C)CC(O)=O WXUAQHNMJWJLTG-VKHMYHEASA-N 0.000 description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-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
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-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
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 150000002170 ethers Chemical class 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 239000003456 ion exchange resin Substances 0.000 description 3
- 229920003303 ion-exchange polymer Polymers 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 229930195734 saturated hydrocarbon Natural products 0.000 description 3
- RNVYQYLELCKWAN-UHFFFAOYSA-N solketal Chemical compound CC1(C)OCC(CO)O1 RNVYQYLELCKWAN-UHFFFAOYSA-N 0.000 description 3
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 3
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 229920006351 engineering plastic Polymers 0.000 description 2
- 150000007529 inorganic bases Chemical class 0.000 description 2
- 150000007530 organic bases Chemical class 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 235000011056 potassium acetate Nutrition 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 description 2
- 229940014800 succinic anhydride Drugs 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- ZCYJBTKNPHKPPN-UHFFFAOYSA-N (2-methyl-1,3-dioxolan-4-yl)methanol Chemical compound CC1OCC(CO)O1 ZCYJBTKNPHKPPN-UHFFFAOYSA-N 0.000 description 1
- BOHGAOWOIJMTPZ-UHFFFAOYSA-N 1,3-dioxolan-4-ylmethanol Chemical compound OCC1COCO1 BOHGAOWOIJMTPZ-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- JPSKCQCQZUGWNM-UHFFFAOYSA-N 2,7-Oxepanedione Chemical compound O=C1CCCCC(=O)O1 JPSKCQCQZUGWNM-UHFFFAOYSA-N 0.000 description 1
- SHKUUQIDMUMQQK-UHFFFAOYSA-N 2-[4-(oxiran-2-ylmethoxy)butoxymethyl]oxirane Chemical compound C1OC1COCCCCOCC1CO1 SHKUUQIDMUMQQK-UHFFFAOYSA-N 0.000 description 1
- ZFIVKAOQEXOYFY-UHFFFAOYSA-N Diepoxybutane Chemical compound C1OC1C1OC1 ZFIVKAOQEXOYFY-UHFFFAOYSA-N 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- QOSMNYMQXIVWKY-UHFFFAOYSA-N Propyl levulinate Chemical compound CCCOC(=O)CCC(C)=O QOSMNYMQXIVWKY-UHFFFAOYSA-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
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 239000012024 dehydrating agents Substances 0.000 description 1
- 150000001990 dicarboxylic acid derivatives Chemical class 0.000 description 1
- 150000004862 dioxolanes Chemical class 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- VANNPISTIUFMLH-UHFFFAOYSA-N glutaric anhydride Chemical compound O=C1CCCC(=O)O1 VANNPISTIUFMLH-UHFFFAOYSA-N 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- KKHUSADXXDNRPW-UHFFFAOYSA-N malonic anhydride Chemical compound O=C1CC(=O)O1 KKHUSADXXDNRPW-UHFFFAOYSA-N 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 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
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
Abstract
Description
【０００１】0001
【産業上の利用分野】本発明は、極性基を持ち、かつト
リオキサンと共重合する新規な１，３−ジオキソラン化
合物に関する。FIELD OF THE INVENTION The present invention relates to a novel 1,3-dioxolane compound having a polar group and copolymerizable with trioxane.
【０００２】0002
【従来の技術】ポリアセタールは機械的強度、熱安定性
、寸法安定性、成形性などの優れた特性を有し、エンジ
ニアリングプラスチックとして、広く利用されている。BACKGROUND OF THE INVENTION Polyacetal has excellent properties such as mechanical strength, thermal stability, dimensional stability, and moldability, and is widely used as an engineering plastic.
【０００３】一方、近年エンジニアリングプラスチック
に対する要求性能が多様化、高度化してきている。ポリ
アセタールに関しても例外ではなく、耐衝撃性、耐摩耗
性、成形加工性等の諸性質が優れたポリアセタールの開
発が望まれており、これまでにいくつかの検討がなされ
ている。耐衝撃性を向上させる方法としてはポリアセタ
ールにポリウレタンを分散させることが知られている。
例えば、最近の例では、特開昭５９−１４５２４３公報
及び特開昭６１−１９６５２公報に、特殊な構造のポリ
ウレタンの分散法が開示されている。また、特開平２−
２９４３５３公報には、１，４−ブタンジオールジグリ
シジルエーテルまたはブタジエンジエポキシドをふくむ
ゴム弾性コポリマーをポリアセタールに添加することに
よって、弾性、接着性を向上させる方法が開示されてい
る。このようにポリアセタールの改良はこれまで盛んに
行われてきており、更に優れたポリアセタールの開発が
望まれている。また、一方では、特開平２−４８４９公
報に開示されているように、ポリエーテルエステルブロ
ック共重合体をポリアセタールに添加し、帯電防止の機
能を付与している。このように、今後は、新しい機能や
、これまでにない性質を持ったポリアセタールの開発が
望まれる。On the other hand, in recent years, the performance requirements for engineering plastics have become more diverse and sophisticated. Polyacetal is no exception, and there is a desire to develop polyacetal with excellent properties such as impact resistance, abrasion resistance, and moldability, and several studies have been made so far. A known method for improving impact resistance is to disperse polyurethane in polyacetal. For example, as a recent example, methods for dispersing polyurethane having a special structure are disclosed in Japanese Patent Application Laid-open Nos. 59-145243 and 61-19652. Also, JP-A-2-
Publication No. 294353 discloses a method of improving elasticity and adhesiveness by adding a rubber elastic copolymer containing 1,4-butanediol diglycidyl ether or butadiene diepoxide to polyacetal. As described above, many efforts have been made to improve polyacetals, and the development of even better polyacetals is desired. On the other hand, as disclosed in JP-A-2-4849, a polyether ester block copolymer is added to polyacetal to impart an antistatic function. Thus, in the future, it is desirable to develop polyacetals with new functions and unprecedented properties.
【０００５】それらを実現する一つの方法としてポリア
セタールに極性基を導入することが有効である。ポリア
セタール鎖に直接、極性基が導入されれば、新しい機能
や性質の付与はより簡便に行われる。[0005] One effective way to achieve these goals is to introduce polar groups into polyacetal. If a polar group is directly introduced into the polyacetal chain, new functions and properties can be imparted more easily.
【０００６】一方、ポリアセタールのコポリマーとして
は、トリオキサンとジオキソラン化合物などとの共重合
体が知られている。ジオキソラン骨格および極性基を持
つ化合物があれば、新しい機能、性質をポリアセタール
に付与するコポリマーの合成が期待できる。On the other hand, as polyacetal copolymers, copolymers of trioxane and dioxolane compounds are known. If we have a compound with a dioxolane skeleton and a polar group, we can expect to synthesize copolymers that add new functions and properties to polyacetal.
【０００７】[0007]
【発明が解決しようとする課題】本発明の課題は、トリ
オキサンと共重合し、かつ、ポリアセタールに極性基を
導入するコモノマーを得ることにある。SUMMARY OF THE INVENTION An object of the present invention is to obtain a comonomer which is copolymerized with trioxane and which introduces a polar group into polyacetal.
【０００８】[0008]
【課題を解決するための手段】本発明者らは、ポリアセ
タールに新しい機能、性質を付与させるのに有効な、ト
リオキサンと共重合するコモノマーを得るべく鋭意検討
した結果、新規な、極性基を持つ１，３−ジオキソラン
化合物を合成し、本発明を完成させた。即ち、本発明は
下記化１で表される化合物に関するものである。[Means for Solving the Problems] As a result of intensive studies to obtain a comonomer that copolymerizes with trioxane and is effective for imparting new functions and properties to polyacetal, the present inventors have discovered a novel comonomer having a polar group. The present invention was completed by synthesizing a 1,3-dioxolane compound. That is, the present invention relates to a compound represented by the following formula 1.
【０００９】[0009]
【化１】[Chemical formula 1]
【００１０】（式中Ｘは炭素数Ｉ〜４の直鎖の飽和また
は不飽和炭化水素を表す。Ｒ１，Ｒ２は、それぞれ独立
に水素またはメチル基、Ｒ３は水素または炭素数１〜４
のアルキル基を示す。）(In the formula, X represents a linear saturated or unsaturated hydrocarbon having I to 4 carbon atoms. R1 and R2 are each independently hydrogen or a methyl group, and R3 is hydrogen or a straight chain saturated or unsaturated hydrocarbon having 1 to 4 carbon atoms.
represents an alkyl group. )
【００１１】化１で表される化合物は、例えば下記の方
法により得ることができる。即ち、グリシドールとジカ
ルボン酸化合物またはジカルボン酸モノエステル化合物
とを、塩基性触媒存在下反応させることにより、化２に
表されるジオール化合物を得る。The compound represented by formula 1 can be obtained, for example, by the following method. That is, a diol compound represented by Chemical Formula 2 is obtained by reacting glycidol with a dicarboxylic acid compound or a dicarboxylic acid monoester compound in the presence of a basic catalyst.
【００１２】0012
【化２】[Case 2]
【００１３】（式中Ｘは炭素数１〜４の直鎖の飽和また
は不飽和炭化水素を表す。Ｒは水素または炭素数１〜４
のアルキル基を示す。）(In the formula, X represents a linear saturated or unsaturated hydrocarbon having 1 to 4 carbon atoms. R is hydrogen or
represents an alkyl group. )
【００１４】本反応に用いることができる塩基性触媒と
しては、トリエチルアミン、ピリジン等の有機塩基、水
酸化ナトリウム、水酸化カリウム、水酸化リチウム、酢
酸カリウム、炭酸ナトリウム、等の無機塩基、及び塩基
性イオン交換樹脂等がある。また、本反応に用いること
ができるジカルボン酸化合物としては、シュウ酸、マロ
ン酸、コハク酸、グルタル酸、アジピン酸、等がある。
本反応に用いることのできるジカルボン酸モノエステル
化合物としては、上記のジカルボン酸化合物のメチルエ
ステル、エチルエステル、プロピルエステル、イソプロ
ピルエステル、ブチルエステル、イソブチルエステル，
ｔ−ブチルエステル等がある。本反応は、無溶媒または
ジエチルエーテル等のエーテル類、ジクロロメタン、ク
ロロホルム等のハロゲン系脂肪族炭化水素類、ベンゼン
、トルエン等の芳香族炭化水素類、好ましくはアセトニ
トリルを溶媒として用いる。本反応は、無溶媒の場合は
、０℃から２５０℃までの温度範囲で行われ、好ましく
は室温から１００℃までの温度範囲で行われる。溶媒を
用いる場合は、０℃から溶媒の沸点までの温度範囲で行
われ、好ましくは室温から溶媒の沸点の温度範囲で行わ
れる。Basic catalysts that can be used in this reaction include organic bases such as triethylamine and pyridine, inorganic bases such as sodium hydroxide, potassium hydroxide, lithium hydroxide, potassium acetate, and sodium carbonate, and basic catalysts. There are ion exchange resins, etc. Furthermore, examples of dicarboxylic acid compounds that can be used in this reaction include oxalic acid, malonic acid, succinic acid, glutaric acid, and adipic acid. Examples of dicarboxylic acid monoester compounds that can be used in this reaction include methyl ester, ethyl ester, propyl ester, isopropyl ester, butyl ester, isobutyl ester,
Examples include t-butyl ester. In this reaction, no solvent is used or ethers such as diethyl ether, halogenated aliphatic hydrocarbons such as dichloromethane and chloroform, aromatic hydrocarbons such as benzene and toluene, and preferably acetonitrile are used as solvents. This reaction is carried out in a temperature range of 0°C to 250°C, preferably in a temperature range of room temperature to 100°C, in the case of no solvent. When a solvent is used, the temperature range is from 0°C to the boiling point of the solvent, preferably from room temperature to the boiling point of the solvent.
【００１５】化２に表されるジオール化合物を、ホルム
アルデヒド、アセトアルデヒド、アセトン等のカルボニ
ル化合物と酸性触媒下反応させることにより、化１に表
される４位に極性基を持つ１，３−ジオキソラン化合物
を得る。本反応に用いることができる酸性触媒としては
、塩酸、硫酸などの無機酸、パラトルエンスルホン酸等
の有機酸、及び酸性のイオン交換樹脂などがある。本反
応に用いることのできる溶媒は、ジエチルエーテル等の
エーテル類、ジクロロメタン、クロロホルム等のハロゲ
ン系脂肪族炭化水素類、ベンゼン、トルエン等の芳香族
炭化水素類、等であるが、好ましくはジクロロメタンを
用いる。本反応は、脱水条件のもと行うこともできる。
即ち、モレキュラーシーブス、硫酸ナトリウム、硫酸マ
グネシウム等の脱水剤を、反応系中またはソックスレー
抽出器中に存在させることにより脱水を行う方法、ディ
ーンスタークなどの分溜管を用いる方法、反応時に蒸留
を行う方法などがある。本反応は、０℃から溶媒の沸点
までの温度範囲で行われ、好ましくは室温から溶媒の沸
点の温度範囲で行われる。By reacting the diol compound represented by Chemical Formula 2 with a carbonyl compound such as formaldehyde, acetaldehyde, or acetone under an acidic catalyst, a 1,3-dioxolane compound having a polar group at the 4-position represented by Chemical Formula 1 can be obtained. get. Examples of acidic catalysts that can be used in this reaction include inorganic acids such as hydrochloric acid and sulfuric acid, organic acids such as para-toluenesulfonic acid, and acidic ion exchange resins. Solvents that can be used in this reaction include ethers such as diethyl ether, halogenated aliphatic hydrocarbons such as dichloromethane and chloroform, and aromatic hydrocarbons such as benzene and toluene. Preferably, dichloromethane is used. use This reaction can also be carried out under dehydration conditions. Namely, there are methods in which dehydration is carried out by allowing a dehydrating agent such as molecular sieves, sodium sulfate, or magnesium sulfate to be present in the reaction system or in a Soxhlet extractor, a method in which a fractionating tube such as a Dean-Stark tube is used, and a method in which distillation is carried out during the reaction. There are methods. This reaction is carried out in a temperature range from 0°C to the boiling point of the solvent, preferably in a temperature range from room temperature to the boiling point of the solvent.
【００１６】また、化１に示される化合物は次の方法に
よっても得ることができる。すなわち４−ヒドロキシメ
チル−１，３−ジオキソランまたは、２，２−ジメチル
−４−ヒドロキシメチル−１，３−ジオキソランまたは
、２−メチル−４−ヒドロキシメチル１，３−ジオキソ
ランを、塩基性触媒のもと、酸無水物と反応させること
により、化１を得る。本反応に用いることができる塩基
性触媒としては、トリエチルアミン、ピリジン等の有機
塩基、水酸化ナトリウム、水酸化カリウム、水酸化リチ
ウム、酢酸カリウム、炭酸ナトリウム、等の無機塩基、
及び塩基性イオン交換樹脂等がある。また、本反応に用
いることができる酸無水物としては、無水マロン酸、無
水コハク酸、無水グルタル酸、無水アジピン酸、等があ
る。本反応は無溶媒で行うことが好ましいが、溶媒とし
てジエチルエーテル等のエーテル類、ジクロロメタン、
クロロホルム等のハロゲン系脂肪族炭化水素類、ベンゼ
ン、トルエン等の芳香族炭化水素類、アセトニトリル、
ジオキソラン、ジオキサン、ジメチルスルホキシド、ジ
メチルホルムアミド等を溶媒として用いてもよい。本反
応は、０℃から溶媒の沸点までの温度範囲で行われ、好
ましくは室温から溶媒の沸点の温度範囲で行われる。The compound shown in Chemical Formula 1 can also be obtained by the following method. That is, 4-hydroxymethyl-1,3-dioxolane, 2,2-dimethyl-4-hydroxymethyl-1,3-dioxolane, or 2-methyl-4-hydroxymethyl-1,3-dioxolane is mixed with a basic catalyst. By reacting with an acid anhydride, compound 1 is obtained. Basic catalysts that can be used in this reaction include organic bases such as triethylamine and pyridine, inorganic bases such as sodium hydroxide, potassium hydroxide, lithium hydroxide, potassium acetate, and sodium carbonate;
and basic ion exchange resins. Further, examples of acid anhydrides that can be used in this reaction include malonic anhydride, succinic anhydride, glutaric anhydride, adipic anhydride, and the like. This reaction is preferably carried out without a solvent, but the solvents used include ethers such as diethyl ether, dichloromethane,
Halogenated aliphatic hydrocarbons such as chloroform, aromatic hydrocarbons such as benzene and toluene, acetonitrile,
Dioxolane, dioxane, dimethylsulfoxide, dimethylformamide, etc. may be used as the solvent. This reaction is carried out in a temperature range from 0°C to the boiling point of the solvent, preferably in a temperature range from room temperature to the boiling point of the solvent.
【００１７】また本反応で得られる化１に表されるカル
ボン酸化合物は、公知の方法により、化１で表されるエ
ステル化合物に導くことができる。以下本発明を実施例
をもって説明する。The carboxylic acid compound represented by Chemical Formula 1 obtained in this reaction can be converted into an ester compound represented by Chemical Formula 1 by a known method. The present invention will be explained below with reference to examples.
【００１８】[0018]
【実施例１】グリシドール１１．１グラム、コハク酸メ
チル１９．８グラムをアセトニトリル５００ミリリット
ル中、トリエチルアミン３グラム存在下６時間加熱還流
し、（１，２−ジヒドロキシプロピル）メチルスクシナ
ートを３０．３グラム得た。（１，２−ジヒドロキシプ
ロピル）メチルスクシナート３０グラムにパラホルムア
ルデヒド３０グラム、パラトルエンスルホン酸３グラム
を加え、ジクロロメタン中２時間加熱還流したのち、酢
酸エチルで抽出することにより（１，３−ジオキソラン
−４−メチル）メチルスクシナートを１８．５グラム得
た。生成物をＮＭＲ，ＩＲ，ＭＡＳＳの各スペクトルに
より確認した。ＮＭＲスペクトルを図１に、ＩＲスペク
トルを図２に示す。また、ＭＡＳＳスペクトルよりＭ＋
Ｈ＋２１９であった。[Example 1] 11.1 g of glycidol and 19.8 g of methyl succinate were heated under reflux in 500 ml of acetonitrile for 6 hours in the presence of 3 g of triethylamine, and 30.8 g of (1,2-dihydroxypropyl)methyl succinate was heated under reflux in the presence of 3 g of triethylamine. I got 3 grams. 30 grams of paraformaldehyde and 3 grams of paratoluenesulfonic acid were added to 30 grams of (1,2-dihydroxypropyl)methyl succinate, heated under reflux in dichloromethane for 2 hours, and then extracted with ethyl acetate. 18.5 grams of dioxolane-4-methyl)methylsuccinate were obtained. The product was confirmed by NMR, IR, and MASS spectra. The NMR spectrum is shown in FIG. 1, and the IR spectrum is shown in FIG. 2. Also, from the MASS spectrum, M+
It was H+219.
【００１９】[0019]
【実施例２】２，２−ジメチル−４−ヒドロキシメチル
−１，３−ジオキソラン６．６グラムと、無水コハク酸
５グラムを６時間、８０℃で攪拌し、（２，２−ジメチ
ル−１，３−ジオキソラン−４−メチル）スクシナート
を定量的に得た。生成物をＮＭＲ，ＩＲ，ＭＡＳＳの各
スペクトルで確認した。ＮＭＲスペクトルを図３に、Ｉ
Ｒスペクトルを図４に示す。また、ＭＡＳＳスペクトル
よりＭ＋２３２であった。[Example 2] 6.6 grams of 2,2-dimethyl-4-hydroxymethyl-1,3-dioxolane and 5 grams of succinic anhydride were stirred at 80°C for 6 hours. , 3-dioxolane-4-methyl) succinate was obtained quantitatively. The product was confirmed by NMR, IR, and MASS spectra. The NMR spectra are shown in Figure 3, I
The R spectrum is shown in FIG. Moreover, it was M+232 from the MASS spectrum.
【００２０】[0020]
【実施例３】２，２−ジメチル−４−ヒドロキシメチル
−１，３−ジオキソラン６．６グラムと、無水マレイン
酸５グラムを６時間、８０℃で撹拌し、（２，２−ジメ
チル−１，３−ジオキソラン−４−メチル）マレイナー
トを定量的に得た。生成物をＮＭＲ，ＩＲ，ＭＡＳＳの
各スペクトルで確認した。ＮＭＲスペクトルを図５に、
ＩＲスペクトルを図６に示す。また、ＭＡＳＳスペクト
ルよりＭ＋Ｈ＋２３１であった。[Example 3] 6.6 grams of 2,2-dimethyl-4-hydroxymethyl-1,3-dioxolane and 5 grams of maleic anhydride were stirred at 80°C for 6 hours. , 3-dioxolane-4-methyl) maleinate was obtained quantitatively. The product was confirmed by NMR, IR, and MASS spectra. The NMR spectrum is shown in Figure 5.
The IR spectrum is shown in FIG. Furthermore, the MASS spectrum showed M+H+231.
【００２１】[0021]
【発明の効果】本発明にある、一般式（１）に表される
、新規な１，３−ジオキソラン化合物は、トリオキサン
と共重合させることによって、ポリアセタールに新しい
機能、性質を付与するのに有効である。Effects of the Invention The novel 1,3-dioxolane compound represented by the general formula (1) in the present invention is effective in imparting new functions and properties to polyacetal by copolymerizing it with trioxane. It is.
【図１】（１，３−ジオキソラン−４−メチル）メチル
スクシナートのＮＭＲスペクトルである。FIG. 1 is an NMR spectrum of (1,3-dioxolane-4-methyl)methylsuccinate.
【図２】（１，３−ジオキソラン−４−メチル）メチル
スクシナートのＩＲスペクトルである。FIG. 2 is an IR spectrum of (1,3-dioxolane-4-methyl)methylsuccinate.
【図３】（２，２−ジメチル−１，３−ジオキソラン−
４−メチル）スクシナートのＮＭＲスペクトルである。[Figure 3] (2,2-dimethyl-1,3-dioxolane-
4-Methyl) succinate NMR spectrum.
【図４】（２，２−ジメチル−１，３−ジオキソラン−
４−メチル）スクシナートのＩＲスペクトルである。[Figure 4] (2,2-dimethyl-1,3-dioxolane-
IR spectrum of 4-methyl)succinate.
【図５】（２，２−ジメチル−１，３−ジオキソラン−
４−メチル）マレイナートのＮＭＲスペクトルである。[Figure 5] (2,2-dimethyl-1,3-dioxolane-
4-Methyl) maleinate NMR spectrum.
【図６】（２，２−ジメチル−１，３−ジオキソラン−
４−メチル）マレイナートのＩＲスペクトルである。[Figure 6] (2,2-dimethyl-1,3-dioxolane-
IR spectrum of 4-methyl)maleinate.
Claims (1)
キソラン誘導体。 【化１】 （式中Ｘは炭素数１〜４の飽和または不飽和炭化水素鎖
を表す。Ｒ１，Ｒ２は、それぞれ独立に水素またはメチ
ル基、Ｒ３は水素または炭素数１〜４のアルキル基を示
す。）[Scope of Claims] [Claim I] A 1,3-dioxolane derivative represented by the following formula 1. [Chemical formula 1] (wherein, )
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3162000A JPH04312582A (en) | 1991-04-08 | 1991-04-08 | New 1,3-dioxolane compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3162000A JPH04312582A (en) | 1991-04-08 | 1991-04-08 | New 1,3-dioxolane compound |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04312582A true JPH04312582A (en) | 1992-11-04 |
Family
ID=15746133
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3162000A Pending JPH04312582A (en) | 1991-04-08 | 1991-04-08 | New 1,3-dioxolane compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04312582A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3507280A4 (en) * | 2016-06-30 | 2020-06-10 | PTT Global Chemical Public Company Limited | Coalescing agent derived from dioxolane derivatives |
-
1991
- 1991-04-08 JP JP3162000A patent/JPH04312582A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3507280A4 (en) * | 2016-06-30 | 2020-06-10 | PTT Global Chemical Public Company Limited | Coalescing agent derived from dioxolane derivatives |
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