JPH069610A - Production of substituted 1,3-dioxolan-2-one derivative - Google Patents
Production of substituted 1,3-dioxolan-2-one derivativeInfo
- Publication number
- JPH069610A JPH069610A JP1535993A JP1535993A JPH069610A JP H069610 A JPH069610 A JP H069610A JP 1535993 A JP1535993 A JP 1535993A JP 1535993 A JP1535993 A JP 1535993A JP H069610 A JPH069610 A JP H069610A
- Authority
- JP
- Japan
- Prior art keywords
- dioxolan
- substituted
- derivative
- phosgene
- hydroxymethyl
- 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
Landscapes
- Plural Heterocyclic Compounds (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、種々の機能材料用合成
中間体、医薬中間体、電子工業分野、一般化学工業で用
いられる高性能溶剤として有用なエーテル結合を側鎖に
もつ置換１,３−ジオキソラン−２−オン誘導体の製法
に関する。TECHNICAL FIELD The present invention relates to a substituent having an ether bond in the side chain, which is useful as a high-performance solvent used in various synthetic intermediates for functional materials, pharmaceutical intermediates, electronics industry, and general chemical industry. It relates to a method for producing a 3-dioxolan-2-one derivative.
【０００２】[0002]
【従来の技術】近年、ヘテロサイクリック化合物、とり
わけ一分子内に環状カーボネート構造と側鎖にメチレン
基を介してエーテル結合を有する化合物が、種々の用
途、例えば導電性を必要とする機能材料として、また表
示素子として電子工業分野や医薬中間体として医薬工業
分野において嘱望されている。2. Description of the Related Art In recent years, heterocyclic compounds, particularly compounds having a cyclic carbonate structure in one molecule and an ether bond through a methylene group in a side chain, have been used as various functional materials such as conductive materials. Further, it is expected to be a display element in the electronic industry field and a pharmaceutical intermediate field in the pharmaceutical industry field.
【０００３】例えば、次式(Ｉ）：For example, the following equation (I):
【化２】 （式中、ＲはＣ1〜Ｃ4のアルキル基を示す)で表わされ
る化合物において、Ｒがメチルである４−メトキシメチ
ル−１,３−ジオキソラン−２−オンが医薬中間体とし
て用いられることが、チェコスロバキア特許第１９６８
６５(１９８１)号明細書に記載されている。この化合物
の製法は、コレクション・チェコスロフ・ケム・コミュ
ン(Ｃollection Ｃzechoslov．Ｃhem．Ｃommun．)第４
３巻(１９７８)第２０６０頁に記載されている。しかし
ながら、この製法ではグリセロールの２つのヒドロキシ
ル基をアセタール化した後、エーテル化を行いアセター
ル開環後、再びカーボネート化すると云う４段階の反応
により製造されており、工業的実用性に乏しい。また、
環状カーボネートの一般的製法として、グリシドールと
炭酸ガスをオートクレーブ中で直接カーボネート化する
方法が考えられる。この方法では２段階でカーボネート
を製造し得るが、この方法では重合物の副生が避けられ
ない。[Chemical 2] (Wherein R represents a C 1 -C 4 alkyl group), 4-methoxymethyl-1,3-dioxolan-2-one in which R is methyl is used as a pharmaceutical intermediate. But Czechoslovak Patent No. 1968
65 (1981). This compound was prepared according to the method described in Collection Czechoslov Chem.
3 (1978) p. 2060. However, in this production method, the two hydroxyl groups of glycerol are acetalized, and then etherified to open the acetal, followed by carbonation again, which is a four-step reaction, which is not industrially practical. Also,
As a general method for producing a cyclic carbonate, a method in which glycidol and carbon dioxide are directly carbonated in an autoclave can be considered. Although the carbonate can be produced in two steps by this method, a by-product of the polymer cannot be avoided by this method.
【０００４】[0004]
【発明が解決しようとする課題】本発明は少ない反応工
程で副生成物の少ない環状カーボネートの製法を提供す
るためになされたものである。SUMMARY OF THE INVENTION The present invention has been made to provide a process for producing a cyclic carbonate containing a small amount of by-products with a small number of reaction steps.
【０００５】[0005]
【課題を解決するための手段】即ち本発明は、グリセリ
ンとホスゲンまたはジエチルカーボネートとの反応によ
って得られる４−ヒドロキシメチル−１,３−ジオキソ
ラン−２−オンをアルキル化することを特徴とする、次
式(Ｉ）：That is, the present invention is characterized in that 4-hydroxymethyl-1,3-dioxolan-2-one obtained by the reaction of glycerin with phosgene or diethyl carbonate is alkylated. The following formula (I):
【化３】 （式中、ＲはＣ1〜Ｃ4のアルキル基を示す)で表わされ
る置換１,３−ジオキソラン−２−オン誘導体の製法に
関する。[Chemical 3] (Wherein R represents a C 1 -C 4 alkyl group) and relates to a method for producing a substituted 1,3-dioxolan-2-one derivative.
【０００６】本発明によれば、グリセリンとホスゲンま
たはジエチルカーボネートとの反応によって得られる４
−ヒドロキシメチル−１,３−ジオキソラン−２−オン
を原料とし、これに通常の方法、例えば、ウイリアムソ
ンのエーテル合成法に従ってハロゲン化アルキルと反応
させることによって前記の式(Ｉ)で表わされる置換１,
３−ジオキソラン−２−オン誘導体を容易に製造するこ
とが出来る。以下、ホスゲンを用いる場合を代表してそ
の反応式を次の式(Ａ)および(Ｂ)に示す:According to the invention, 4 obtained by the reaction of glycerin with phosgene or diethyl carbonate
-Hydroxymethyl-1,3-dioxolan-2-one is used as a starting material, and this is reacted with an alkyl halide according to a conventional method, for example, Williamson's ether synthesis method, to carry out the substitution represented by the above formula (I). 1,
A 3-dioxolan-2-one derivative can be easily produced. The reaction formulas are shown in the following formulas (A) and (B) on behalf of the case of using phosgene:
【０００７】[0007]
【化４】 [Chemical 4]
【化５】 [Chemical 5]
【０００８】塩基としては水素化ナトリウム、炭酸ナト
リウム、重炭酸ナトリウム、炭酸カリウム、カリウム−
t−ブトキシド等が例示される。また、原料として用い
るハロゲン化アルキルの炭素数は限定しないが低い凝固
点と粘度、高い誘電率を有する化合物を得るためには、
(Ｃ1〜Ｃ4)が好ましい。As the base, sodium hydride, sodium carbonate, sodium bicarbonate, potassium carbonate, potassium-
T-butoxide and the like are exemplified. The number of carbon atoms of the alkyl halide used as a raw material is not limited, but in order to obtain a compound having a low freezing point, a high viscosity and a high dielectric constant,
(C 1 ~C 4) is preferable.
【０００９】上記の反応によって得られる生成物の精製
法は限定的ではないが、例えば、適当な溶媒(メチルエ
チルケトンなど)にて生成物を抽出し、蒸留することに
より、通常約９０％以上の収率で４−アルコキシメチル
−１,３−ジオキソラン−２−オンが得られる。The method for purifying the product obtained by the above reaction is not limited, but, for example, by extracting the product with an appropriate solvent (such as methyl ethyl ketone) and distilling the product, the yield of about 90% or more is usually obtained. The yield is 4-alkoxymethyl-1,3-dioxolan-2-one.
【００１０】[0010]
【実施例】以下、本発明を実施例によって説明する。実施例１ グリセリン９２g(１モル)とピリジン３１６g(４モル)を
１lの滴下ロート、冷却管、撹拌機付四つ口フラスコに
入れ、１５〜２０℃の温度で激しく撹拌しながらホスゲ
ンを１０９g(１．１モル)を徐々に通じ、更に、室温で
３時間撹拌を続け反応を完結させた。反応混合物からピ
リジンの塩酸塩を濾別し、過剰のピリジンを留去した
後、蒸留により４−ヒドロキシメチル−１,３−ジオキ
ソラン−２−オン(８５℃〜９０℃／０．４mmＨg)１１
５g(収率８３％)を得た。EXAMPLES The present invention will be described below with reference to examples. Example 1 92 g (1 mol) of glycerin and 316 g (4 mol) of pyridine were placed in a 1-liter four-necked flask equipped with a dropping funnel, a condenser and a stirrer, and 109 g of phosgene was vigorously stirred at a temperature of 15 to 20 ° C. 1.1 mol) was gradually passed through, and stirring was continued at room temperature for 3 hours to complete the reaction. After removing the pyridine hydrochloride from the reaction mixture by filtration and distilling off excess pyridine, 4-hydroxymethyl-1,3-dioxolan-2-one (85 ° C to 90 ° C / 0.4 mmHg) 11 was obtained by distillation.
5 g (yield 83%) was obtained.
【００１１】得られた４−ヒドロキシメチル−１,３−
ジオキソラン−２−オン１１５g(０．８３モル)、t−ブ
タノール３００ml、カリウムt−ブトキシド９３g(０．
８３モル)を１lの滴下ロート、冷却器、撹拌機付四つ口
フラスコに入れ充分均一になるまで撹拌した後、ヨウ化
メチル１３０g(０．９２モル)を冷却下(１０℃〜２０
℃)に滴下し、滴下終了後３時間、室温で撹拌を続け、
反応完結後ヨウ化カリウムを濾別し、濾液を氷水に注
ぎ、エーテルにて生成物を抽出し、蒸留により１０５℃
〜１０６℃／０．９mmＨgの留分１０７g(収率８５％)を
得た。この化合物の物理特性を次の表１に示す。The obtained 4-hydroxymethyl-1,3-
115 g (0.83 mol) of dioxolan-2-one, 300 ml of t-butanol, 93 g of potassium t-butoxide (0.
(83 mol) was placed in a 1-liter dropping funnel, a condenser and a four-necked flask equipped with a stirrer and stirred until sufficiently uniform, and then 130 g (0.92 mol) of methyl iodide was cooled (10 ° C to 20 ° C).
(° C), and after stirring for 3 hours, continue stirring at room temperature for 3 hours.
After completion of the reaction, potassium iodide was filtered off, the filtrate was poured into ice water, the product was extracted with ether, and distilled at 105 ° C.
107 g (yield 85%) of a fraction of ˜106 ° C./0.9 mmHg was obtained. The physical properties of this compound are shown in Table 1 below.
【００１２】[0012]
【表１】 [Table 1]
【００１３】[0013]
【発明の効果】本発明による置換１,３−ジオキソラン
−２−オン誘導体の製造方法は、４段階を要した従来法
に比し、２段階の反応により、製造工程を著しく短縮す
ることが出来、精製も簡単で高純度の生成物が得られ
る。本発明方法による生成物は、種々の機能を与えるヘ
テロサイクリックな構造を分子内に有し、しかも側鎖に
エーテル結合を持つ極めて誘電率の高い液体であり、有
機化合物だけでなく、無機化合物を溶質として高濃度に
溶解することが出来、優れた電気特性を示すので、液状
高誘電体、有機導電液として利用し得るものである。The method for producing a substituted 1,3-dioxolan-2-one derivative according to the present invention can significantly shorten the production process by the two-step reaction as compared with the conventional method which requires four steps. Purification is easy and a highly pure product can be obtained. The product obtained by the method of the present invention is a liquid having an extremely high dielectric constant, which has a heterocyclic structure that gives various functions in the molecule and has an ether bond in the side chain, and is not only an organic compound but also an inorganic compound. Since it can be dissolved as a solute at a high concentration and exhibits excellent electric characteristics, it can be used as a liquid high dielectric material or an organic conductive liquid.
Claims (1)
ーボネートとの反応によって得られる４−ヒドロキシメ
チル−１,３−ジオキソラン−２−オンをアルキル化す
ることを特徴とする、次式(Ｉ): 【化１】 (式中、ＲはＣ1〜Ｃ4のアルキル基を示す)で表わされる
置換１,３−ジオキソラン−２−オン誘導体の製法。1. The following formula (I), characterized in that 4-hydroxymethyl-1,3-dioxolan-2-one obtained by the reaction of glycerin with phosgene or diethyl carbonate is alkylated: ] (In the formula, R represents a C 1 -C 4 alkyl group) A process for producing a substituted 1,3-dioxolan-2-one derivative.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1535993A JPH0794450B2 (en) | 1993-02-02 | 1993-02-02 | Process for producing substituted 1,3-dioxolan-2-one derivative |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1535993A JPH0794450B2 (en) | 1993-02-02 | 1993-02-02 | Process for producing substituted 1,3-dioxolan-2-one derivative |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP25579285A Division JPS62114985A (en) | 1985-11-13 | 1985-11-13 | Production of substituted 1,3-dioxolan-2-one derivatibe |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH069610A true JPH069610A (en) | 1994-01-18 |
| JPH0794450B2 JPH0794450B2 (en) | 1995-10-11 |
Family
ID=11886611
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1535993A Expired - Fee Related JPH0794450B2 (en) | 1993-02-02 | 1993-02-02 | Process for producing substituted 1,3-dioxolan-2-one derivative |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0794450B2 (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6315918B1 (en) | 1997-09-11 | 2001-11-13 | Mitsui Chemicals Inc. | Non-aqueous electrolytic solution for capacitor and capacitor containing non-aqueous electrolytic solution |
| JP2006504708A (en) * | 2002-10-01 | 2006-02-09 | ビーエーエスエフ アクチェンゲゼルシャフト | Alkyl glycidol carbonate as cosurfactant |
| JP2007039347A (en) * | 2005-08-01 | 2007-02-15 | Kao Corp | Method for producing glycerol carbonate |
| KR100686203B1 (en) * | 2004-08-27 | 2007-02-22 | 삼성정밀화학 주식회사 | Method for preparing phenylthio-1,3-dioxoran-2-one derivative |
| KR100686204B1 (en) * | 2004-08-27 | 2007-02-23 | 삼성정밀화학 주식회사 | Method for preparing phenyloxo-1,3-dioxolan-2-one derivative |
| WO2010001673A1 (en) | 2008-06-30 | 2010-01-07 | ダイキン工業株式会社 | Manufacturing method for fluoropropylene carbonate |
| WO2013189861A1 (en) | 2012-06-19 | 2013-12-27 | Akzo Nobel Chemicals International B.V. | Process for the preparation of cyclic organic carbonates |
| US9000204B2 (en) | 2009-07-16 | 2015-04-07 | Solvay Flour Gmbh | Process for the preparation of fluoroalkyl (fluoro)alkyl carbonates and carbamates |
-
1993
- 1993-02-02 JP JP1535993A patent/JPH0794450B2/en not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6315918B1 (en) | 1997-09-11 | 2001-11-13 | Mitsui Chemicals Inc. | Non-aqueous electrolytic solution for capacitor and capacitor containing non-aqueous electrolytic solution |
| JP2006504708A (en) * | 2002-10-01 | 2006-02-09 | ビーエーエスエフ アクチェンゲゼルシャフト | Alkyl glycidol carbonate as cosurfactant |
| JP4778232B2 (en) * | 2002-10-01 | 2011-09-21 | ビーエーエスエフ ソシエタス・ヨーロピア | Alkyl glycidol carbonate as cosurfactant |
| KR100686203B1 (en) * | 2004-08-27 | 2007-02-22 | 삼성정밀화학 주식회사 | Method for preparing phenylthio-1,3-dioxoran-2-one derivative |
| KR100686204B1 (en) * | 2004-08-27 | 2007-02-23 | 삼성정밀화학 주식회사 | Method for preparing phenyloxo-1,3-dioxolan-2-one derivative |
| JP2007039347A (en) * | 2005-08-01 | 2007-02-15 | Kao Corp | Method for producing glycerol carbonate |
| WO2010001673A1 (en) | 2008-06-30 | 2010-01-07 | ダイキン工業株式会社 | Manufacturing method for fluoropropylene carbonate |
| US9000204B2 (en) | 2009-07-16 | 2015-04-07 | Solvay Flour Gmbh | Process for the preparation of fluoroalkyl (fluoro)alkyl carbonates and carbamates |
| WO2013189861A1 (en) | 2012-06-19 | 2013-12-27 | Akzo Nobel Chemicals International B.V. | Process for the preparation of cyclic organic carbonates |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0794450B2 (en) | 1995-10-11 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |