JP5200428B2 - Method for producing tetrahydropyran-4-one - Google Patents
Method for producing tetrahydropyran-4-one Download PDFInfo
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- JP5200428B2 JP5200428B2 JP2007156186A JP2007156186A JP5200428B2 JP 5200428 B2 JP5200428 B2 JP 5200428B2 JP 2007156186 A JP2007156186 A JP 2007156186A JP 2007156186 A JP2007156186 A JP 2007156186A JP 5200428 B2 JP5200428 B2 JP 5200428B2
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- JMJRYTGVHCAYCT-UHFFFAOYSA-N oxan-4-one Chemical compound O=C1CCOCC1 JMJRYTGVHCAYCT-UHFFFAOYSA-N 0.000 title claims description 20
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- LMYJGUNNJIDROI-UHFFFAOYSA-N oxan-4-ol Chemical compound OC1CCOCC1 LMYJGUNNJIDROI-UHFFFAOYSA-N 0.000 claims description 16
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical group OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 14
- 150000002978 peroxides Chemical class 0.000 claims description 7
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 claims description 7
- AAQNGTNRWPXMPB-UHFFFAOYSA-N dipotassium;dioxido(dioxo)tungsten Chemical compound [K+].[K+].[O-][W]([O-])(=O)=O AAQNGTNRWPXMPB-UHFFFAOYSA-N 0.000 claims description 3
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 description 21
- 238000000034 method Methods 0.000 description 11
- 239000000243 solution Substances 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 4
- 150000007522 mineralic acids Chemical class 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-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
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- QWMFKVNJIYNWII-UHFFFAOYSA-N 5-bromo-2-(2,5-dimethylpyrrol-1-yl)pyridine Chemical compound CC1=CC=C(C)N1C1=CC=C(Br)C=N1 QWMFKVNJIYNWII-UHFFFAOYSA-N 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000003905 agrochemical Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- LEHBURLTIWGHEM-UHFFFAOYSA-N pyridinium chlorochromate Chemical compound [O-][Cr](Cl)(=O)=O.C1=CC=[NH+]C=C1 LEHBURLTIWGHEM-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 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 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-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
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 235000013877 carbamide Nutrition 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- PODWXQQNRWNDGD-UHFFFAOYSA-L sodium thiosulfate pentahydrate Chemical compound O.O.O.O.O.[Na+].[Na+].[O-]S([S-])(=O)=O PODWXQQNRWNDGD-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
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- Pyrane Compounds (AREA)
Description
本発明は、テトラヒドロピラン−４−オンを製造する方法に関する。テトラヒドロピラン−４−オンは、例えば、医薬・農薬等の原料や合成中間体として有用な化合物である（例えば、特許文献１参照）。 The present invention relates to a process for producing tetrahydropyran-4-one. Tetrahydropyran-4-one is, for example, a compound useful as a raw material for pharmaceuticals and agricultural chemicals or a synthetic intermediate (see, for example, Patent Document 1).
従来、テトラヒドロピラン−４−オールからテトラヒドロピラン−４−オンを製造する方法としては、例えば、テトラヒドロピラン−４−オールとクロロクロム酸ピリジニウムとを塩化メチレン中で反応させる方法（例えば、非特許文献１参照）やテトラヒドロピラン−４−オールとフッ素とを反応させる方法が知られている（例えば、非特許文献２参照）。しかしながら、これらの製法においては、毒性が高い酸化剤や取り扱いが難しいフッ素の使用をしなければならず、テトラヒドロピラン−４−オンの工業的な製法としては満足するものではなかった。 Conventionally, as a method for producing tetrahydropyran-4-one from tetrahydropyran-4-ol, for example, a method of reacting tetrahydropyran-4-ol and pyridinium chlorochromate in methylene chloride (for example, non-patent literature) 1) or tetrahydropyran-4-ol and fluorine are known (for example, see Non-Patent Document 2). However, in these production methods, it is necessary to use a highly toxic oxidizing agent or fluorine which is difficult to handle, and this is not satisfactory as an industrial production method of tetrahydropyran-4-one.
本発明の課題は、即ち、上記問題点を解決し、温和な条件下、環境調和型で簡便な方法によって、テトラヒドロピラン−４−オールから、テトラヒドロピラン−４−オンを製造できる、工業的に好適なテトラヒドロピラン−４−オンの製法を提供することにある。 The problem to be solved by the present invention is to solve the above-mentioned problems and industrially produce tetrahydropyran-4-one from tetrahydropyran-4-ol by an environmentally friendly and simple method under industrial conditions. The object is to provide a process for producing a suitable tetrahydropyran-4-one.
本発明の課題は、テトラヒドロピラン−４−オール、タングステン酸塩、過酸化物とを反応させることを特徴とする、テトラヒドロピラン−４−オンの製法によって解決される The object of the present invention is solved by a process for producing tetrahydropyran-4-one, characterized by reacting tetrahydropyran-4-ol, tungstate, and peroxide.
本発明により、温和な条件下、簡便な方法によって、テトラヒドロピラン−４−オールから、テトラヒドロピラン−４−オンを高収率で製造できる。なお、その際、過酸化物として使用する過酸化水素は、反応にて水へと変換することができることから、工業的、かつ環境調和型で好適なテトラヒドロピラン−４−オンの製法を提供することができる。 According to the present invention, tetrahydropyran-4-one can be produced in high yield from tetrahydropyran-4-ol by a simple method under mild conditions. In this case, since hydrogen peroxide used as a peroxide can be converted into water by reaction, an industrial and environmentally friendly method for producing tetrahydropyran-4-one is provided. be able to.
本発明の過酸化物は、過酸化水素を使用することが望ましい。その際、過酸化水素は水溶液でも、あるいは、反応に関与しない溶媒と混合して使用してもよい。さらにその溶媒は、単独、又は二種以上を使用しても良い。 The peroxide of the present invention preferably uses hydrogen peroxide. In this case, hydrogen peroxide may be used as an aqueous solution or mixed with a solvent that does not participate in the reaction. Further, the solvent may be used alone or in combination of two or more.
前記過酸化物の使用量は、テトラヒドロピラン−４−オール１モルに対して、好ましくは０．７〜５モル、更に好ましくは１〜３モルで、特に好ましくは１〜２モルである。 The amount of the peroxide used is preferably 0.7 to 5 mol, more preferably 1 to 3 mol, and particularly preferably 1 to 2 mol with respect to 1 mol of tetrahydropyran-4-ol.
本発明の反応において使用するタングステン酸塩としては、例えば、タングステン酸ナトリウム、タングステン酸カリウム、タングステン酸カルシウム等が挙げられるが、好ましくはタングステン酸ナトリウム、タングステン酸カリウムが使用され、更に好ましくはタングステン酸ナトリウムが使用される。なお、これらのタングステン酸塩は水和物でもよく、さらに単独又は二種以上を混合して使用しても良い。 Examples of the tungstate used in the reaction of the present invention include sodium tungstate, potassium tungstate, and calcium tungstate, preferably sodium tungstate and potassium tungstate are used, and more preferably tungstic acid. Sodium is used. In addition, these tungstates may be hydrates, and may be used alone or in admixture of two or more.
前記タングステン酸塩の使用量は、テトラヒドロピラン−４−オール１モルに対して、好ましくは０．０００５〜０．０５モル、更に好ましくは０．００１〜０．０１モルである。 The amount of the tungstate used is preferably 0.0005 to 0.05 mol, more preferably 0.001 to 0.01 mol, per 1 mol of tetrahydropyran-4-ol.
本発明の反応においては、無機酸を添加しても良い。無機酸としては、例えば、リン酸、硫酸、塩酸等が挙げられるが、好ましくはリン酸が使用される。なお、これらの無機酸は水溶液でもよく、単独または二種以上を混合して使用しても良い。 In the reaction of the present invention, an inorganic acid may be added. Examples of the inorganic acid include phosphoric acid, sulfuric acid, hydrochloric acid and the like, and phosphoric acid is preferably used. These inorganic acids may be aqueous solutions, or may be used alone or in combination of two or more.
前記無機酸の使用量は、テトラヒドロピラン−４−オール１モルに対して、好ましくは０〜０．１モル、更に好ましくは０〜０．０５モルである。 The amount of the inorganic acid used is preferably 0 to 0.1 mol, more preferably 0 to 0.05 mol, per 1 mol of tetrahydropyran-4-ol.
本発明の反応は溶媒の存在下又は非存在下において行われる。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、水；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；メチルエチルケトン、メチルイソブチルケトン等のケトン類；トルエン、キシレン等の芳香族炭化水素類が挙げられるが、好ましくは水、ケトン類、更に好ましくは水が使用される。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 carried out in the presence or absence of a solvent. The solvent to be used is not particularly limited as long as it does not inhibit the reaction. For example, water; amides such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone; N, N′— Examples include ureas such as dimethylimidazolidinone; ketones such as methyl ethyl ketone and methyl isobutyl ketone; and aromatic hydrocarbons such as toluene and xylene, preferably water, ketones, and more preferably water. 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、テトラヒドロピラン−４−オール１．０ｇに対して、好ましくは０〜５０ｍｌ、更に好ましくは０〜１０ｍｌ、特に好ましくは０〜２ｍｌである。 The amount of the solvent used is appropriately adjusted depending on the homogeneity and stirrability of the reaction solution. 0-2 ml.
本発明の反応は、例えば、テトラヒドロピラン−４−オールとタングステン酸塩と過酸化物とを混合して、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５０〜１５０℃、更に好ましくは８０〜１２０℃である。なお、その際、反応圧力は特に制限されない。 The reaction of the present invention is performed by, for example, a method of mixing tetrahydropyran-4-ol, tungstate, and peroxide and reacting them while stirring. The reaction temperature in that case becomes like this. Preferably it is 50-150 degreeC, More preferably, it is 80-120 degreeC. At that time, the reaction pressure is not particularly limited.
なお、反応生成物であるテトラヒドロピラン−４−オンは、反応終了後、例えば、抽出、濃縮、蒸留、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。 The reaction product, tetrahydropyran-4-one, is isolated and purified by a general method such as extraction, concentration, distillation, column chromatography, etc. after completion of the reaction.
本発明の好ましい態様としては、テトラヒドロピラン−４−オールとタングステン酸塩との混合液に、５０〜１５０℃にて攪拌しながら過酸化水素を加えて反応させる等の方法によって行われる。その際、反応圧力は特に制限されない。 As a preferred embodiment of the present invention, it is carried out by a method such as adding hydrogen peroxide to a mixed solution of tetrahydropyran-4-ol and tungstate at 50 to 150 ° C. with stirring to react. At that time, the reaction pressure is not particularly limited.
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（テトラヒドロピラン−４−オンの合成）
攪拌装置、滴下漏斗及び温度計を備えた内容積２００ｍｌのガラス製耐圧容器に、テトラヒドロピラン−４−オール６０．１ｇ(０．５８８ｍｏｌ)とタングステン酸ナトリウム二水和物０．９７３ｇ(０．００２９５ｍｏｌ)とを加えた混合液を９０℃に加熱し、次いで３４．５質量％過酸化水素水溶液１１６ｇ（１．１８ｍｏｌ）を加え、液温８４〜９３℃で攪拌しながら６時間反応させた。反応終了後、反応液に２０質量％チオ硫酸ナトリウム水溶液３８．４ｇとチオ硫酸ナトリウム五水和物１９．７ｇを加えた。この溶液を、ガスクロマトグラフィー（内部標準検量法）で分析したところ、反応溶液にはテトラヒドロピラン−４−オンが４３．９ｇ生成していた（反応収率；７４％）。
引き続き、この反応溶液の一部（７９．５ｇ）を、塩化メチレンを用いて抽出した後、これを濃縮した。得られた濃縮物を減圧蒸留（８８〜９２℃／７．３ｋＰa）することにより、テトラヒドロピラン−４−オン１１．７ｇを得た（テトラヒドロピラン−４−オール基準の単離収率；５６％）。
Example 1 (Synthesis of tetrahydropyran-4-one)
In a 200-ml glass pressure vessel equipped with a stirrer, dropping funnel and thermometer, 60.1 g (0.588 mol) tetrahydropyran-4-ol and 0.973 g (0.00295 mol) sodium tungstate dihydrate were added. ) Was heated to 90 ° C., then 116 g (1.18 mol) of 34.5 mass% hydrogen peroxide aqueous solution was added, and the mixture was reacted at a liquid temperature of 84 to 93 ° C. with stirring for 6 hours. After completion of the reaction, 38.4 g of a 20% by mass aqueous sodium thiosulfate solution and 19.7 g of sodium thiosulfate pentahydrate were added to the reaction solution. When this solution was analyzed by gas chromatography (internal standard calibration method), 43.9 g of tetrahydropyran-4-one was produced in the reaction solution (reaction yield; 74%).
Subsequently, a part of the reaction solution (79.5 g) was extracted with methylene chloride, and then concentrated. The obtained concentrate was distilled under reduced pressure (88-92 ° C./7.3 kPa) to obtain 11.7 g of tetrahydropyran-4-one (isolated yield based on tetrahydropyran-4-ol; 56% ).
実施例２（テトラヒドロピラン−４−オンの合成）
攪拌装置、滴下漏斗及び温度計を備えた内容積３０ｍｌのガラス製耐圧容器に、テトラヒドロピラン−４−オール３．１ｇ(３０ｍｍｏｌ)、タングステン酸ナトリウム二水和物０．０４９ｇ(０．１５ｍｍｏｌ)、８５質量％リン酸０．０６０ｇ(０．５２ｍｍｏｌ)との混合液を８０℃に加熱し、次いで３４．５質量％過酸化水素水溶液４．１ｇ（４２ｍｍｏｌ）を加え、液温７５〜８９℃で攪拌しながら６時間反応させた。反応終了後、得られた反応溶液を分析したところ、テトラヒドロピラン−４−オンが反応収率約５５％で生成していた。
Example 2 (Synthesis of tetrahydropyran-4-one)
In a 30-ml glass pressure vessel equipped with a stirrer, a dropping funnel and a thermometer, 3.1 g (30 mmol) of tetrahydropyran-4-ol, 0.049 g (0.15 mmol) of sodium tungstate dihydrate, A liquid mixture with 85 mass% phosphoric acid 0.060 g (0.52 mmol) was heated to 80 ° C, then 4.1 g (42 mmol) of 34.5 mass% hydrogen peroxide aqueous solution was added, and the liquid temperature was 75-89 ° C. The reaction was allowed to proceed for 6 hours with stirring. When the obtained reaction solution was analyzed after completion of the reaction, tetrahydropyran-4-one was produced at a reaction yield of about 55%.
本発明は、テトラヒドロピラン−４−オールから、テトラヒドロピラン−４−オンを製造する方法に関する。テトラヒドロピラン−４−オンは、例えば、医薬・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 a process for producing tetrahydropyran-4-one from tetrahydropyran-4-ol. Tetrahydropyran-4-one is a useful compound, for example, as a raw material for pharmaceuticals, agricultural chemicals, and synthetic intermediates.
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|---|---|---|---|
| JP2007156186A JP5200428B2 (en) | 2007-06-13 | 2007-06-13 | Method for producing tetrahydropyran-4-one |
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| Application Number | Priority Date | Filing Date | Title |
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| JP2007156186A JP5200428B2 (en) | 2007-06-13 | 2007-06-13 | Method for producing tetrahydropyran-4-one |
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| Publication Number | Publication Date |
|---|---|
| JP2008308419A JP2008308419A (en) | 2008-12-25 |
| JP5200428B2 true JP5200428B2 (en) | 2013-06-05 |
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