JP2006249004A - 2-(4-cyanotetrahydropyran-4-yl)-2-oxoacetic acid ester and method for producing the same - Google Patents
2-(4-cyanotetrahydropyran-4-yl)-2-oxoacetic acid ester and method for producing the same Download PDFInfo
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Abstract
Description
本発明は、2-(4-シアノテトラヒドロピラン-4-イル)-2-オキソ酢酸エステル及びその製法に関する。2-(4-シアノテトラヒドロピラン-4-イル)-2-オキソ酢酸エステルは、医薬や農薬等の原料や合成中間体として有用な化合物である。 The present invention relates to 2- (4-cyanotetrahydropyran-4-yl) -2-oxoacetic acid ester and a method for producing the same. 2- (4-Cyanotetrahydropyran-4-yl) -2-oxoacetate is a useful compound as a raw material and synthetic intermediate for pharmaceuticals and agricultural chemicals.
本発明の2-(4-シアノテトラヒドロピラン-4-イル)-2-オキソ酢酸エステルは、新規な化合物であり、従来までにその存在や製法は全く知られていなかった。 The 2- (4-cyanotetrahydropyran-4-yl) -2-oxoacetic acid ester of the present invention is a novel compound, and its existence and production method have never been known so far.
本発明の課題は、即ち、上記問題点を解決し、簡便な方法によって、2-(4-シアノテトラヒドロピラン-4-イル)-2-オキソ酢酸エステルを高収率で製造出来る、工業的に好適な2-(4-シアノテトラヒドロピラン-4-イル)-2-オキソ酢酸エステル及びその製法を提供することである。 The object of the present invention is to solve the above-mentioned problems and industrially produce 2- (4-cyanotetrahydropyran-4-yl) -2-oxoacetic acid ester in a high yield by a simple method. It is to provide a suitable 2- (4-cyanotetrahydropyran-4-yl) -2-oxoacetic acid ester and a process for its preparation.
前記課題に鑑み、本発明者らが鋭意検討を行った結果、以下に示す簡便な方法によって2-(4-シアノテトラヒドロピラン-4-イル)-2-オキソ酢酸エステルを高収率で製造出来る方法を見出し、本発明を完成させた。 In view of the above problems, as a result of intensive studies by the present inventors, 2- (4-cyanotetrahydropyran-4-yl) -2-oxoacetate can be produced in a high yield by the following simple method. A method was found and the present invention was completed.
即ち、本発明の課題は、一般式（１） That is, the subject of this invention is general formula (1).
（式中、Ｒは、炭化水素基を示す。）
で示される2-(4-シアノテトラヒドロピラン-4-イル)-2-オキソ酢酸エステル（以下、化合物（１）と称する）によって解決される。
(In the formula, R represents a hydrocarbon group.)
It is solved by 2- (4-cyanotetrahydropyran-4-yl) -2-oxoacetic acid ester (hereinafter referred to as compound (1)).
本発明の課題は、又、塩基の存在下、4-シアノテトラヒドロピランと一般式（２） Another object of the present invention is to provide 4-cyanotetrahydropyran and general formula (2) in the presence of a base.
（式中、Ｘは、ハロゲン原子、アルコキシ基、アラルキルオキシ基又はアリールオキシ基を示し、Ｒは、前記と同義である。）
で示されるシュウ酸化合物（以下、化合物（２）と称する）とを反応させることを特徴とする、一般式（１）
(In the formula, X represents a halogen atom, an alkoxy group, an aralkyloxy group or an aryloxy group, and R has the same meaning as described above.)
And an oxalic acid compound (hereinafter referred to as compound (2)) represented by the general formula (1)
（式中、Ｒは、前記と同義である。）
で示される化合物（１）の製法によっても解決される。
(In the formula, R is as defined above.)
It can also be solved by the production method of the compound (1) represented by formula (1).
本発明により、簡便な方法によって、2-(4-シアノテトラヒドロピラン-4-イル)-2-オキソ酢酸エステルを高収率で製造することが可能であり、且つ、工業的に好適な2-(4-シアノテトラヒドロピラン-4-イル)-2-オキソ酢酸エステル及びその製法を提供することが出来る。 According to the present invention, 2- (4-cyanotetrahydropyran-4-yl) -2-oxoacetic acid ester can be produced in a high yield by a simple method, and industrially suitable 2- (4-Cyanotetrahydropyran-4-yl) -2-oxoacetic acid ester and a production method thereof can be provided.
本発明の新規な化合物（１）は、前記の一般式（１）で示される。その一般式（１）において、Ｒは、炭化水素基であり、具体的には、例えば、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基等のアルキル基；シクロプロピル基、シクロブチル基、シクロペンチル基、シクロヘキシル基、シクロヘプチル基、シクロオクチル基、シクロノニル基、シクロデシル基等のシクロアルキル基；ベンジル基、フェネチル基等のアラルキル基；フェニル基、トリル基、キシリル基、ナフチル基等のアリール基が挙げられるが、好ましくはメチル基、エチル基である。なお、これらの基は、各種異性体を含む。 The novel compound (1) of the present invention is represented by the general formula (1). In the general formula (1), R is a hydrocarbon group, specifically, for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group. Alkyl groups such as decyl group; cycloalkyl groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecyl group; aralkyl groups such as benzyl group and phenethyl group; An aryl group such as a phenyl group, a tolyl group, a xylyl group, and a naphthyl group is exemplified, and a methyl group and an ethyl group are preferable. These groups include various isomers.
本発明の化合物（１）は、塩基の存在下、4-シアノテトラヒドロピランと前記の化合物（２）とを反応させることによって得られる。 The compound (1) of the present invention can be obtained by reacting 4-cyanotetrahydropyran with the compound (2) in the presence of a base.
本発明の反応において使用する化合物（２）は、前記の一般式（２）で示される。その一般式（２）において、Ｘは、フッ素原子、塩素原子、臭素原子、ヨウ素原子等のハロゲン原子；メトキシ基、エトキシ基、プロポキシ基、ブトキシ基等のアルコキシ基；ベンジルオキシ基、フェネチルオキシ基等のアラルキルオキシ基；フェノキシ基等のアリールオキシ基が挙げられるが、好ましくはハロゲン原子、アルコキシ基、更に好ましくはメトキシ基、エトキシ基である。なお、これらの基は、各種異性体を含む。又、Ｒは、前記と同義である。 The compound (2) used in the reaction of the present invention is represented by the general formula (2). In the general formula (2), X is a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom; an alkoxy group such as a methoxy group, an ethoxy group, a propoxy group or a butoxy group; a benzyloxy group or a phenethyloxy group Aralkyloxy groups such as phenoxy group and the like, and aryloxy groups such as phenoxy group are preferable, and a halogen atom, an alkoxy group, and more preferably a methoxy group and an ethoxy group. These groups include various isomers. R is as defined above.
本発明の反応において使用する塩基としては、例えば、水酸化ナトリウム、水酸化カリウム等のアルカリ金属水酸化物；炭酸ナトリウム、炭酸カリウム等のアルカリ金属炭酸塩；炭酸水素ナトリウム、炭酸水素カリウム等のアルカリ金属炭酸水素塩；ナトリウムメトキシド、ナトリウムエトキシド等のアルカリ金属アルコキシド；水素化ナトリウム、水素化カリウム等のアルカリ金属水素化物；メチルリチウム、n-ブチルリチウム、sec-ブチルリチウム、t-ブチルリチウム等のアルカリ金属アルキル；リチウムジイソプロピルアミド、リチウムビス(トリメチルシリル)アミド、ナトリウムアミド、ナトリウムビス(トリメチルシリル)アミド等のアルカリ金属アミドが挙げられるが、好ましくはアルカリ金属アミド、更に好ましくはリチウムビス(トリメチルシリル)アミドが使用される。なお、これらの塩基は、単独又は二種以上を混合して使用しても良い。 Examples of the base used in the reaction of the present invention include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; alkali metal carbonates such as sodium carbonate and potassium carbonate; alkalis such as sodium hydrogen carbonate and potassium hydrogen carbonate Metal bicarbonates; alkali metal alkoxides such as sodium methoxide and sodium ethoxide; alkali metal hydrides such as sodium hydride and potassium hydride; methyl lithium, n-butyl lithium, sec-butyl lithium, t-butyl lithium, etc. Alkali metal amides such as lithium diisopropylamide, lithium bis (trimethylsilyl) amide, sodium amide, sodium bis (trimethylsilyl) amide, and the like. Limethylsilyl) amide is used. In addition, you may use these bases individually or in mixture of 2 or more types.
前記塩基の使用量は、4-シアノテトラヒドロピラン1モルに対して、好ましくは0.8〜5.0モル、更に好ましくは1.0〜2.0モルである。 The amount of the base used is preferably 0.8 to 5.0 mol, more preferably 1.0 to 2.0 mol, per 1 mol of 4-cyanotetrahydropyran.
本発明の反応は、溶媒中にて行われるのが好ましく、使用する溶媒としては、反応を阻害しないものならば特に限定されず、例えば、トリエチルアミン、トリブチルアミン等のアミン類；ピリジン、メチルピリジン、ジメチルアミノピリジン等のピリジン類；キノリン、イソキノリン、メチルイソキノリン等のキノリン類；N,N-ジメチルホルムアミド、N,N-ジメチルアセトアミド、N-メチルピロリドン等のアミド類；N,N'-ジメチルイミダゾリジノン等の尿素類；ジメチルスルホキシド、スルホラン等のスルホキシド類；n-プロピルアルコール、n-ブチルアルコール等のアルコール類；ジエチルエーテル、テトラヒドロフラン、ジメトキシエタン、ジイソプロピルエーテル、ジオキサン、シクロプロピルメチルエーテル等のエーテル類；トルエン、キシレン等の芳香族炭化水素類；酢酸エチル、酢酸ブチル等のカルボン酸エステル類が挙げられるが、好ましくはエーテル類、芳香族炭化水素類が使用される。なお、これらの溶媒は、単独又は二種以上を混合して使用しても良い。 The reaction of the present invention is preferably carried out in a solvent, and the solvent to be used is not particularly limited as long as it does not inhibit the reaction. For example, amines such as triethylamine and tributylamine; pyridine, methylpyridine, Pyridines such as dimethylaminopyridine; Quinolines such as quinoline, isoquinoline and methylisoquinoline; Amides such as N, N-dimethylformamide, N, N-dimethylacetamide and N-methylpyrrolidone; N, N'-dimethylimidazolid Ureas such as non; sulfoxides such as dimethyl sulfoxide and sulfolane; alcohols such as n-propyl alcohol and n-butyl alcohol; ethers such as diethyl ether, tetrahydrofuran, dimethoxyethane, diisopropyl ether, dioxane and cyclopropyl methyl ether ; Toluene, Ki Aromatic hydrocarbons such as silene; carboxylic acid esters such as ethyl acetate and butyl acetate are exemplified, and ethers and aromatic hydrocarbons are preferably used. In addition, you may use these solvents individually or in mixture of 2 or more types.
前記溶媒の使用量は、反応液の均一性や攪拌性により適宜調節するが、4-シアノテトラヒドロピラン1gに対して、好ましくは0.5〜50g、更に好ましくは1〜20gである。 The amount of the solvent used is appropriately adjusted depending on the uniformity and stirrability of the reaction solution, but is preferably 0.5 to 50 g, more preferably 1 to 20 g, relative to 1 g of 4-cyanotetrahydropyran.
本発明の反応は、例えば、4-シアノテトラヒドロピラン、化合物（２）及び塩基を混合し、攪拌しながら反応させる等の方法によって行われる。その際の反応温度は、好ましくは-100〜150℃、更に好ましくは-50〜120℃であり、反応圧力は特に制限されない。 The reaction of the present invention is performed, for example, by a method of mixing 4-cyanotetrahydropyran, compound (2) and a base and reacting them with stirring. The reaction temperature at that time is preferably -100 to 150 ° C, more preferably -50 to 120 ° C, and the reaction pressure is not particularly limited.
なお、本発明の反応によって化合物（１）が得られるが、これは、反応終了後、中和、抽出、濾過、濃縮、蒸留、再結晶、晶析、カラムクロマトグラフィー等の一般的な方法によって単離・精製される。 Compound (1) is obtained by the reaction of the present invention, and this is carried out by a general method such as neutralization, extraction, filtration, concentration, distillation, recrystallization, crystallization, column chromatography after completion of the reaction. Isolated and purified.
次に、実施例を挙げて本発明を具体的に説明するが、本発明の範囲はこれらに限定されるものではない。 Next, the present invention will be specifically described with reference to examples, but the scope of the present invention is not limited thereto.
実施例１（化合物（１）［Ｒ＝エチル基］；2-(4-シアノテトラヒドロピラン-4-イル)-2-オキソ酢酸エチルの合成）
攪拌装置、温度計及び滴下漏斗を備えた内容積100mlのガラス製フラスコに、1.0mol/lリチウムビス(トリメチルシリル)アミドのテトラヒドロフラン溶液56.7ml(56.8mmol)を加え、液温を-10〜0℃に維持しながら、4-シアノテトラヒドロピラン6.0g(54.0mmol)を滴下し、同温度で1時間攪拌させた。次いで、シュウ酸ジエチル18.7g(135mmol)を滴下し、攪拌しながら同温度で1時間反応させた。反応終了後、反応液の温度を0℃以下に保ちながら、ギ酸3.72g(81mmol)を加え1時間攪拌した後、アセトニトリル26mlを加えた。析出した固体を濾過し、濾液を減圧下で濃縮した後、濃縮物をシリカゲルカラムクロマトグラフィーで精製（展開溶媒；ヘキサン/酢酸エチル＝9/1→7/3）し、黄色液体として、2-(4-シアノテトラヒドロピラン-4-イル)-2-オキソ酢酸エチル3.78gを得た（単離収率；33％）。
2-(4-シアノテトラヒドロピラン-4-イル)-2-オキソ酢酸エチルは、以下の物性値で示される新規な化合物である。
Example 1 (Compound (1) [R = ethyl group]; Synthesis of ethyl 2- (4-cyanotetrahydropyran-4-yl) -2-oxoacetate)
To a glass flask having an internal volume of 100 ml equipped with a stirrer, a thermometer and a dropping funnel, 56.7 ml (56.8 mmol) of 1.0 mol / l lithium bis (trimethylsilyl) amide in tetrahydrofuran was added, and the liquid temperature was −10 to 0 ° C. Then, 6.0 g (54.0 mmol) of 4-cyanotetrahydropyran was added dropwise, and the mixture was stirred at the same temperature for 1 hour. Next, 18.7 g (135 mmol) of diethyl oxalate was added dropwise and reacted at the same temperature for 1 hour with stirring. After completion of the reaction, while maintaining the temperature of the reaction solution at 0 ° C. or lower, 3.72 g (81 mmol) of formic acid was added and stirred for 1 hour, and then 26 ml of acetonitrile was added. The precipitated solid was filtered, and the filtrate was concentrated under reduced pressure. The concentrate was purified by silica gel column chromatography (developing solvent; hexane / ethyl acetate = 9/1 → 7/3) to give 2- 3.78 g of ethyl (4-cyanotetrahydropyran-4-yl) -2-oxoacetate was obtained (isolation yield; 33%).
2- (4-Cyanotetrahydropyran-4-yl) -2-oxoacetic acid ethyl is a novel compound represented by the following physical properties.
1H-NMR(CDCl3,δ(ppm))；1.42(3H,t,J=7.2Hz)、2.08〜2.14(4H,m)、3.76〜3.85(2H,m)、4.00〜4.06(2H,m)、4.42(2H,q,J=7.2Hz)
CI-MS(m/e)；212(M+1)
1 H-NMR (CDCl 3 , δ (ppm)); 1.42 (3H, t, J = 7.2 Hz), 2.08 to 2.14 (4H, m), 3.76 to 3.85 (2H, m), 4.00 to 4.06 (2H, m), 4.42 (2H, q, J = 7.2Hz)
CI-MS (m / e); 212 (M + 1)
本発明は、2-(4-シアノテトラヒドロピラン-4-イル)-2-オキソ酢酸エステル及びその製法に関する。2-(4-シアノテトラヒドロピラン-4-イル)-2-オキソ酢酸エステルは、医薬や農薬等の原料や合成中間体として有用な化合物である。 The present invention relates to 2- (4-cyanotetrahydropyran-4-yl) -2-oxoacetic acid ester and a method for producing the same. 2- (4-Cyanotetrahydropyran-4-yl) -2-oxoacetate is a useful compound as a raw material and synthetic intermediate for pharmaceuticals and agricultural chemicals.
Claims (2)
で示される2-(4-シアノテトラヒドロピラン-4-イル)-2-オキソ酢酸エステル。 General formula (1)
2- (4-Cyanotetrahydropyran-4-yl) -2-oxoacetic acid ester represented by
で示されるシュウ酸化合物とを反応させることを特徴とする、一般式（１）
で示される2-(4-シアノテトラヒドロピラン-4-イル)-2-オキソ酢酸エステルの製法。 4-cyanotetrahydropyran and general formula (2) in the presence of a base
A reaction with an oxalic acid compound represented by the general formula (1):
2- (4-Cyanotetrahydropyran-4-yl) -2-oxoacetic acid ester represented by
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| JP2006249005A (en) * | 2005-03-11 | 2006-09-21 | Ube Ind Ltd | Method for producing 2-(tetrahydropyran-4-yl)-2-oxoacetic acid |
| JP2006249004A (en) * | 2005-03-11 | 2006-09-21 | Ube Ind Ltd | 2-(4-cyanotetrahydropyran-4-yl)-2-oxoacetic acid ester and method for producing the same |
| EP1903427A2 (en) | 2006-09-14 | 2008-03-26 | Hitachi, Ltd. | Storage apparatus and configuration setting method |
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| JP2006249004A (en) * | 2005-03-11 | 2006-09-21 | Ube Ind Ltd | 2-(4-cyanotetrahydropyran-4-yl)-2-oxoacetic acid ester and method for producing the same |
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| JP2006249004A (en) * | 2005-03-11 | 2006-09-21 | Ube Ind Ltd | 2-(4-cyanotetrahydropyran-4-yl)-2-oxoacetic acid ester and method for producing the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006249005A (en) * | 2005-03-11 | 2006-09-21 | Ube Ind Ltd | Method for producing 2-(tetrahydropyran-4-yl)-2-oxoacetic acid |
| JP2006249004A (en) * | 2005-03-11 | 2006-09-21 | Ube Ind Ltd | 2-(4-cyanotetrahydropyran-4-yl)-2-oxoacetic acid ester and method for producing the same |
| EP1903427A2 (en) | 2006-09-14 | 2008-03-26 | Hitachi, Ltd. | Storage apparatus and configuration setting method |
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