JP7060753B1 - Method for producing 2-acetyltetrahydropyridine compound - Google Patents
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- -1 2-acetyltetrahydropyridine compound Chemical class 0.000 title claims abstract description 57
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 27
- 239000003960 organic solvent Substances 0.000 claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- RXKJFZQQPQGTFL-UHFFFAOYSA-N dihydroxyacetone Chemical compound OCC(=O)CO RXKJFZQQPQGTFL-UHFFFAOYSA-N 0.000 claims abstract description 18
- ONIBWKKTOPOVIA-BYPYZUCNSA-N L-Proline Chemical compound OC(=O)[C@@H]1CCCN1 ONIBWKKTOPOVIA-BYPYZUCNSA-N 0.000 claims abstract description 15
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims abstract description 14
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims abstract description 14
- 238000003756 stirring Methods 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 11
- ONIBWKKTOPOVIA-UHFFFAOYSA-N Proline Natural products OC(=O)C1CCCN1 ONIBWKKTOPOVIA-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims description 19
- 238000009835 boiling Methods 0.000 claims description 12
- HRAOWRVFLSYJKN-UHFFFAOYSA-N 6-acetyl-1,2,3,4-tetrahydropyridine Chemical compound CC(=O)C1=CCCCN1 HRAOWRVFLSYJKN-UHFFFAOYSA-N 0.000 claims description 9
- 238000001577 simple distillation Methods 0.000 claims description 7
- GNZWXNKZMHJXNU-UHFFFAOYSA-N 6-acetyl-2,3,4,5-tetrahydropyridine Chemical compound CC(=O)C1=NCCCC1 GNZWXNKZMHJXNU-UHFFFAOYSA-N 0.000 claims description 3
- 238000010586 diagram Methods 0.000 abstract 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 42
- 239000002994 raw material Substances 0.000 description 21
- 229960002429 proline Drugs 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- 238000004821 distillation Methods 0.000 description 7
- 239000003205 fragrance Substances 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- 229930182821 L-proline Natural products 0.000 description 5
- 235000013305 food Nutrition 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000000796 flavoring agent Substances 0.000 description 2
- 235000019634 flavors Nutrition 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000008267 milk Substances 0.000 description 2
- 235000013336 milk Nutrition 0.000 description 2
- 210000004080 milk Anatomy 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- URAYPUMNDPQOKB-UHFFFAOYSA-N triacetin Chemical compound CC(=O)OCC(OC(C)=O)COC(C)=O URAYPUMNDPQOKB-UHFFFAOYSA-N 0.000 description 2
- 239000004375 Dextrin Substances 0.000 description 1
- 229920001353 Dextrin Polymers 0.000 description 1
- DOOTYTYQINUNNV-UHFFFAOYSA-N Triethyl citrate Chemical compound CCOC(=O)CC(O)(C(=O)OCC)CC(=O)OCC DOOTYTYQINUNNV-UHFFFAOYSA-N 0.000 description 1
- 229940024606 amino acid Drugs 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000008162 cooking oil Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- GVJHHUAWPYXKBD-UHFFFAOYSA-N d-alpha-tocopherol Natural products OC1=C(C)C(C)=C2OC(CCCC(C)CCCC(C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-UHFFFAOYSA-N 0.000 description 1
- 235000019425 dextrin Nutrition 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 238000007701 flash-distillation Methods 0.000 description 1
- 235000013312 flour Nutrition 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 239000001087 glyceryl triacetate Substances 0.000 description 1
- 235000013773 glyceryl triacetate Nutrition 0.000 description 1
- 230000000873 masking effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000011403 purification operation Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229940079827 sodium hydrogen sulfite Drugs 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229960001295 tocopherol Drugs 0.000 description 1
- 229930003799 tocopherol Natural products 0.000 description 1
- 235000010384 tocopherol Nutrition 0.000 description 1
- 239000011732 tocopherol Substances 0.000 description 1
- 229960002622 triacetin Drugs 0.000 description 1
- 239000001069 triethyl citrate Substances 0.000 description 1
- VMYFZRTXGLUXMZ-UHFFFAOYSA-N triethyl citrate Natural products CCOC(=O)C(O)(C(=O)OCC)C(=O)OCC VMYFZRTXGLUXMZ-UHFFFAOYSA-N 0.000 description 1
- 235000013769 triethyl citrate Nutrition 0.000 description 1
- GVJHHUAWPYXKBD-IEOSBIPESA-N α-tocopherol Chemical compound OC1=C(C)C(C)=C2O[C@@](CCC[C@H](C)CCC[C@H](C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-IEOSBIPESA-N 0.000 description 1
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Abstract
【課題】２－アセチルテトラヒドロピリジン化合物を安価にかつ簡便に製造する方法を提供すること。【解決手段】特定の有機溶媒中でプロリン、１，３－ジヒドロキシアセトン及び亜硫酸水素ナトリウムを特定の反応温度で攪拌混合して反応させることを特徴とする２－アセチルテトラヒドロピリジン化合物の製造方法。【選択図】なしPROBLEM TO BE SOLVED: To provide a method for producing a 2-acetyltetrahydropyridine compound inexpensively and easily. A method for producing a 2-acetyltetrahydropyridine compound, which comprises stirring and mixing proline, 1,3-dihydroxyacetone and sodium bisulfite at a specific reaction temperature in a specific organic solvent. [Selection diagram] None
Description
本発明は、香料成分として有用な２－アセチルテトラヒドロピリジン化合物の工業的な製造方法に関する。 The present invention relates to an industrial method for producing a 2-acetyltetrahydropyridine compound useful as a fragrance component.
２－アセチルテトラヒドロピリジン化合物の製造方法として、いくつかの方法が存在するが、いずれも自然発火性物質、禁水性物質、自己反応性物質など危険物に指定される原料を使用する、製造工程数が多い、収率が低く経済性が低いなど、工業的に製造する上で課題があった。 There are several methods for producing 2-acetyltetrahydropyridine compounds, all of which use raw materials designated as dangerous substances such as pyrophoric substances, water-reactive materials, and self-reactive substances, and the number of production steps. There were problems in industrial production, such as high yield and low economic efficiency.
たとえば、特許文献１記載の方法は、亜硫酸水素ナトリウム、L－プロリン、１，３－ジヒドロキシアセトンを紛体混合して、８０～１００℃で３０分間反応させることを特徴とするが、紛体で混合するため反応中に原料が固化するため収率が低いという課題があった。特許文献１に倣って当該化合物を合成したところ、単蒸留後の収率は１．８％、純度は８０．５％であった。 For example, the method described in Patent Document 1 is characterized in that sodium hydrogen sulfite, L-proline, and 1,3-dihydroxyacetone are mixed in a powder and reacted at 80 to 100 ° C. for 30 minutes, but the powder is mixed. Therefore, there is a problem that the yield is low because the raw material solidifies during the reaction. When the compound was synthesized according to Patent Document 1, the yield after simple distillation was 1.8% and the purity was 80.5%.
特許文献２記載の方法は、発火性原料を使用するため製造上の問題があり、収率も低いという課題があった。
特許文献３記載の方法は、発火性原料を使用するため製造上の問題があり、反応の工程数が多く、収率も低いという課題があった。
特許文献４記載の方法は、発火性原料を使用するため製造上の課題があった。
The method described in Patent Document 2 has a problem in manufacturing because it uses an ignitable raw material, and has a problem that the yield is low.
The method described in Patent Document 3 has a problem in manufacturing because it uses an ignitable raw material, and has a problem that the number of reaction steps is large and the yield is low.
The method described in Patent Document 4 has a problem in manufacturing because it uses an ignitable raw material.
非特許文献１記載の方法は、発火性原料を使用するため製造上の課題があった。
非特許文献２、３記載の方法は、いずれも発火性原料を使用するため製造上の問題があり、さらに反応の工程数が多いという課題があった。
非特許文献４、５記載の方法はいずれも高価な原料から合成反応を開始するため、経済的に課題があった。
The method described in Non-Patent Document 1 has a problem in manufacturing because it uses an ignitable raw material.
All of the methods described in Non-Patent Documents 2 and 3 have a problem in manufacturing because they use an ignitable raw material, and also have a problem that the number of reaction steps is large.
All of the methods described in Non-Patent Documents 4 and 5 have a problem economically because the synthetic reaction is started from an expensive raw material.
また、特許文献５記載の方法は、プロリン、糖類、穀粉、アルカリ剤、水、食用油を加熱して得られる、２－アセチルテトラヒドロピリジン化合物を有効成分として含む風味付与剤の製造方法であるが、２－アセチルテトラヒドロピリジン化合物の収率及び反応後の精製に課題があった。 Further, the method described in Patent Document 5 is a method for producing a flavor-imparting agent containing a 2-acetyltetrahydropyridine compound as an active ingredient, which is obtained by heating proline, sugar, cereal flour, alkaline agent, water, and cooking oil. , 2-Acetyltetrahydropyridine There was a problem in the yield of the compound and purification after the reaction.
一方、２－アセチルテトラヒドロピリジン化合物は、香料原料として非常に有益な成分で、この香料成分を安価に大量に製造する方法が望まれていた。
特許文献６には、２－アセチルテトラヒドロピリジン化合物に風味付与効果があることが記載され、特許文献７には乳風味飲食品のコク味増強効果があることが記載されている。
また、特許文献８には、２－アセチルテトラヒドロピリジン化合物がデキストリンや加熱臭をマスキングする効果があることが記載されている。
このように、２－アセチルテトラヒドロピリジン化合物については、香料成分として飲食品に対する様々な効果が報告されている。
On the other hand, the 2-acetyltetrahydropyridine compound is a very useful component as a fragrance raw material, and a method for inexpensively producing a large amount of this fragrance component has been desired.
Patent Document 6 describes that the 2-acetyltetrahydropyridine compound has a flavor-imparting effect, and Patent Document 7 describes that it has an effect of enhancing the richness of milk-flavored foods and drinks.
Further, Patent Document 8 describes that the 2-acetyltetrahydropyridine compound has an effect of masking dextrin and a heated odor.
As described above, the 2-acetyltetrahydropyridine compound has been reported to have various effects on foods and drinks as a flavoring component.
本発明の目的は、従来技術の欠点を解消し、有用化合物である２－アセチルテトラヒドロピリジン化合物を安価、簡便、安全かつ高い収率で製造する方法を提供することである。 An object of the present invention is to eliminate the drawbacks of the prior art and to provide a method for producing a useful compound 2-acetyltetrahydropyridine compound at low cost, convenience, safety and in high yield.
本発明者は、従来知られている公知の方法を工業スケールで実施する際の課題について整理した。
表１に示すように、工業原料としては高価な原料の使用、発火性、爆発性のある危険物に分類される原料の使用、製造に特殊な設備が必要、収率の低さなど、いずれの方法でも工業的生産に適さない、すなわち安価で安定的に供給する点において課題があることが明確になった。
The present inventor has organized the problems in implementing the conventionally known and known methods on an industrial scale.
As shown in Table 1, the use of expensive raw materials as industrial raw materials, the use of raw materials classified as ignitable and explosive dangerous goods, the need for special equipment for manufacturing, low yield, etc. It has become clear that even this method is not suitable for industrial production, that is, there is a problem in that it is inexpensive and stable in supply.
そこで、汎用的で発火性のない原料のみを使用して、収率の高い合成方法を検討した。
有機溶媒中で、安価で汎用的な原料で作業安全上の懸念が無い亜硫酸水素ナトリウム、Ｌ－プロリン、１，３－ジヒドロキシアセトンのみを原料として使い、これらを加熱反応と蒸留するだけの簡単な合成方法を検討した。
鋭意検討の結果、反応で使用する有機溶媒を検討した結果、下記の条件（ａ）～（ｄ）に適合する有機溶媒を使用し、反応温度を設定した場合に限り、２－アセチルテトラヒドロピリジン化合物を収率良く合成できることを見出した。
なお、本発明において、２－アセチルテトラヒドロピリジン化合物は、２－アセチル－３，４，５，６－テトラヒドロピリジン、２－アセチル－１，４，５，６－テトラヒドロピリジンのいずれか又は双方を含む化合物である。
Therefore, we investigated a high-yield synthesis method using only general-purpose, non-ignitable raw materials.
In an organic solvent, only sodium bisulfite, L-proline, and 1,3-dihydroxyacetone, which are inexpensive and general-purpose raw materials and have no work safety concerns, are used as raw materials, and these are simply heated and distilled. The synthesis method was examined.
As a result of diligent studies, as a result of studying the organic solvent used in the reaction, the 2-acetyltetrahydropyridine compound was used only when the reaction temperature was set by using the organic solvent suitable for the following conditions (a) to (d). Was found to be able to be synthesized in good yield.
In the present invention, the 2-acetyltetrahydropyridine compound contains either or both of 2-acetyl-3,4,5,6-tetrahydropyridine and 2-acetyl-1,4,5,6-tetrahydropyridine. It is a compound.
（ａ）有機溶媒の常圧での沸点（Ｘ℃）と攪拌混合させる反応温度（Ｙ℃）の差（Ｘ－Ｙ）が７０℃以上２００℃以下になるように有機溶媒及び反応温度を選択する。
（ｂ）攪拌混合させる反応温度を５０℃を超えて８０℃以下の範囲内で選択する。
（ｃ）沸点が１５０℃以上３００℃以下である有機溶媒を選択する。
（ｄ）比誘電率が３０以上１００以下である有機溶媒を選択する。
(A) Select the organic solvent and reaction temperature so that the difference (XY) between the boiling point (X ° C.) of the organic solvent at normal pressure and the reaction temperature (Y ° C.) for stirring and mixing is 70 ° C. or higher and 200 ° C. or lower. do.
(B) The reaction temperature for stirring and mixing is selected within the range of more than 50 ° C and 80 ° C or less.
(C) Select an organic solvent having a boiling point of 150 ° C. or higher and 300 ° C. or lower.
(D) Select an organic solvent having a relative permittivity of 30 or more and 100 or less.
すなわち、本発明は以下のとおりである。
〔１〕有機溶媒中でプロリン、１，３－ジヒドロキシアセトン及び亜硫酸水素ナトリウムを攪拌混合して反応させることによって２－アセチルテトラヒドロピリジン化合物を製造する方法であって、
（ａ）有機溶媒の常圧での沸点（Ｘ℃）と攪拌混合させる反応温度（Ｙ℃）の差（Ｘ－Ｙ）が７０℃以上２００℃以下になるように有機溶媒及び反応温度を選択すること、及び、
（ｂ）攪拌混合させる反応温度を５０℃を超えて８０℃以下の範囲内で選択すること、
を特徴とし、
ここで、２－アセチルテトラヒドロピリジン化合物は、２－アセチル－３，４，５，６－テトラヒドロピリジン、２－アセチル－１，４，５，６－テトラヒドロピリジンのいずれか一方又は双方を含むこと、
を特徴とする２－アセチルテトラヒドロピリジン化合物の製造方法。
That is, the present invention is as follows.
[1] A method for producing a 2-acetyltetrahydropyridine compound by stirring and mixing proline, 1,3-dihydroxyacetone and sodium bisulfite in an organic solvent and reacting them.
(A) Select the organic solvent and reaction temperature so that the difference (XY) between the boiling point (X ° C.) of the organic solvent at normal pressure and the reaction temperature (Y ° C.) for stirring and mixing is 70 ° C. or higher and 200 ° C. or lower. What to do and
(B) Select the reaction temperature for stirring and mixing within the range of more than 50 ° C and 80 ° C or less.
Characterized by
Here, the 2-acetyltetrahydropyridine compound comprises either or both of 2-acetyl-3,4,5,6-tetrahydropyridine and 2-acetyl-1,4,5,6-tetrahydropyridine.
A method for producing a 2-acetyltetrahydropyridine compound.
〔２〕常圧での沸点が１５０℃以上３００℃以下である有機溶媒を選択することを特徴とする、上記１の２－アセチルテトラヒドロピリジン化合物の製造方法。
〔３〕比誘電率が３０以上１００以下である有機溶媒を選択することを特徴とする、上記１又は２の２－アセチルテトラヒドロピリジン化合物の製造方法。
[2] The method for producing a 2-acetyltetrahydropyridine compound according to 1 above, which comprises selecting an organic solvent having a boiling point of 150 ° C. or higher and 300 ° C. or lower at normal pressure.
[3] The method for producing a 2-acetyltetrahydropyridine compound according to 1 or 2 above, which comprises selecting an organic solvent having a relative permittivity of 30 or more and 100 or less.
〔４〕有機溶媒が、Ｎ，Ｎ－ジメチルホルムアミド、エチレンカーボネート、ジメチルスルホキシド及びＮ，Ｎ－ジメチルアセトアミドからなる群より選ばれた少なくとも１種である上記１～３のいずれかに記載の２－アセチルテトラヒドロピリジン化合物の製造方法。 [4] The 2-described in any one of 1 to 3 above, wherein the organic solvent is at least one selected from the group consisting of N, N-dimethylformamide, ethylene carbonate, dimethyl sulfoxide and N, N-dimethylacetamide. A method for producing an acetyltetrahydropyridine compound.
〔５〕上記の方法で製造された２－アセチルテトラヒドロピリジン化合物を、さらに単蒸留によって精製することを特徴とする上記１～４のいずれかに記載の２－アセチルテトラヒドロピリジン化合物の製造方法。
〔６〕上記１～５のいずれかに記載の方法で製造された２－アセチルテトラヒドロピリジン化合物を有効成分とする香料組成物。
[5] The method for producing a 2-acetyltetrahydropyridine compound according to any one of 1 to 4 above, wherein the 2-acetyltetrahydropyridine compound produced by the above method is further purified by simple distillation.
[6] A fragrance composition containing a 2-acetyltetrahydropyridine compound produced by the method according to any one of 1 to 5 above as an active ingredient.
本発明の方法によれば、香料成分、特に飲食品用香料として有用な２－アセチルテトラヒドロピリジン化合物を安価、簡便、安全かつ高い収率で製造することができる。 According to the method of the present invention, a flavoring component, particularly a 2-acetyltetrahydropyridine compound useful as a flavoring for foods and drinks, can be produced inexpensively, easily, safely and in a high yield.
以下、本発明の２－アセチルテトラヒドロピリジン化合物の製造方法について、詳細に説明する。
〔１〕原材料
２－アセチルテトラヒドロピリジン化合物を合成するため使用する原材料は、プロリン、１，３－ジヒドロキシアセトン及び亜硫酸水素ナトリウムである。
プロリンは、アミノ酸として市販されている工業用途のＬ－プロリンを適宜使用することができる。
１，３－ジヒドロキシアセトンは、市販されている工業用途の１，３－ジヒドロキシアセトンを適宜使用することができ、同様に亜硫酸水素ナトリウムについても市販されている工業用途の亜硫酸水素ナトリウムを適宜使用することができる。
Hereinafter, the method for producing the 2-acetyltetrahydropyridine compound of the present invention will be described in detail.
[1] Raw Materials The raw materials used for synthesizing the 2-acetyltetrahydropyridine compound are proline, 1,3-dihydroxyacetone and sodium bisulfite.
As proline, L-proline for industrial use, which is commercially available as an amino acid, can be appropriately used.
As the 1,3-dihydroxyacetone, commercially available industrial 1,3-dihydroxyacetone can be appropriately used, and similarly, as for sodium bisulfite, commercially available sodium bisulfite for industrial use is appropriately used. be able to.
各原材料の配合比は、好ましくは、１，３－ジヒドロキシアセトン１モルに対し、プロリンが１～５モル、亜硫酸水素ナトリウムが１～５モルとなるように使用する。
より好ましくは１，３－ジヒドロキシアセトン１モルに対し、プロリンが１～３モル、亜硫酸水素ナトリウムが２～４モルであり、更に好ましくは１，３－ジヒドロキシアセトン１モルに対し、プロリン１．５～２．５モルと亜硫酸水素ナトリウム２～３モルとなるように使用する。
The compounding ratio of each raw material is preferably 1 to 5 mol of proline and 1 to 5 mol of sodium bisulfite with respect to 1 mol of 1,3-dihydroxyacetone.
More preferably, 1 to 3 mol of proline and 2 to 4 mol of sodium bisulfite are used with respect to 1 mol of 1,3-dihydroxyacetone, and more preferably 1.5 mol of proline is used with respect to 1 mol of 1,3-dihydroxyacetone. It is used so as to be ~ 2.5 mol and 2 ~ 3 mol of sodium bisulfite.
〔２〕有機溶媒
本発明で使用する有機溶媒は、常圧での沸点が１５０℃以上３００℃以下である有機溶媒が好ましい。
さらに、２０～４０℃の比誘電率が３０以上１００以下である有機溶媒を使用することが好ましい。ここで、物質のなかの電気変位（電束密度）Ｄと電場Ｅの関係Ｄ＝εＥで与えられる係数εを誘電率といい、真空の誘電率ε0との比（ε／ε0）を比誘電率という。
[2] Organic Solvent The organic solvent used in the present invention is preferably an organic solvent having a boiling point of 150 ° C. or higher and 300 ° C. or lower at normal pressure.
Further, it is preferable to use an organic solvent having a relative permittivity of 30 to 40 ° C. of 30 or more and 100 or less. Here, the coefficient ε given by the relationship D = εE between the electric displacement (electric flux density) D and the electric field E in the substance is called the permittivity, and the ratio (ε / ε 0 ) to the permittivity ε 0 of the vacuum is called the permittivity. It is called the relative permittivity.
上記の条件を満たす好適な有機溶媒として、Ｎ，Ｎ－ジメチルホルムアミド（沸点１５３℃；比誘電率３６．７（２５℃））、エチレンカーボネート（沸点２４８℃；比誘電率８９．８（４０℃））、ジメチルスルホキシド（沸点１８９℃；比誘電率４６．５（２５℃））、Ｎ，Ｎ－ジメチルアセトアミド（沸点１６５℃；比誘電率３７．８（２５℃））があり、これらを１種又は２種以上併用することができる。 Suitable organic solvents that satisfy the above conditions include N, N-dimethylformamide (boiling point 153 ° C.; relative permittivity 36.7 (25 ° C.)) and ethylene carbonate (boiling point 248 ° C.; relative permittivity 89.8 (40 ° C.)). )), Dimethyl sulfoxide (boiling point 189 ° C; relative permittivity 46.5 (25 ° C)), N, N-dimethylacetamide (boiling point 165 ° C; relative permittivity 37.8 (25 ° C)). Seeds or two or more can be used in combination.
有機溶媒の使用量は、好ましくは１，３－ジヒドロキシアセトン１モルに対し１～１０Ｌ、より好ましく１，３－ジヒドロキシアセトン１モルに対し１～６Ｌ、さらに好ましくは１，３－ジヒドロキシアセトン１モルに対し１～３Ｌとなるように使用する。 The amount of the organic solvent used is preferably 1 to 10 L per 1 mol of 1,3-dihydroxyacetone, more preferably 1 to 6 L per 1 mol of 1,3-dihydroxyacetone, and even more preferably 1 mol of 1,3-dihydroxyacetone. It is used so that it becomes 1 to 3 L.
〔３〕反応条件
攪拌混合させる反応温度を５０℃を超えて８０℃以下の範囲で選択する。
有機溶媒の沸点と反応温度の差が７０℃以上２００℃以下になるように選択した有機溶媒と、亜硫酸水素ナトリウム、Ｌ-プロリン、１，３－ジヒドロキシアセトンを所定量混合し加熱撹拌する。
攪拌装置は、特に限定されないが、一般的なマグネティックスターラー、メカニカルスターラーや、ニーダー、ディスパーザー、混合ミル、ラインミキサー、乳化機等、特に限定されず使用できる。
[3] Reaction conditions The reaction temperature for stirring and mixing is selected in the range of more than 50 ° C and 80 ° C or less.
A predetermined amount of sodium bisulfite, L-proline, and 1,3-dihydroxyacetone are mixed with an organic solvent selected so that the difference between the boiling point of the organic solvent and the reaction temperature is 70 ° C. or higher and 200 ° C. or lower, and the mixture is heated and stirred.
The stirring device is not particularly limited, but can be used without particular limitation, such as a general magnetic stirrer, a mechanical stirrer, a kneader, a disperser, a mixing mill, a line mixer, an emulsifier, and the like.
加熱攪拌する時間は、好ましくは０．５～５時間で、より好ましくは０．５～３時間、さらに好ましくは１～２時間が好ましい。
また、５０℃以下では合成反応が進まず、８０℃を超えると副反応が起こるため２－アセチルテトラヒドロピリジン化合物の収率が低くなる。したがって、反応温度は５０℃を超えて８０℃以下が好ましく、より好ましくは５５℃～８０℃、さらに好ましくは６０℃～８０℃が好ましい。
The heating and stirring time is preferably 0.5 to 5 hours, more preferably 0.5 to 3 hours, still more preferably 1 to 2 hours.
Further, the synthetic reaction does not proceed at 50 ° C. or lower, and a side reaction occurs at 80 ° C. or higher, so that the yield of the 2-acetyltetrahydropyridine compound is low. Therefore, the reaction temperature is preferably more than 50 ° C. and preferably 80 ° C. or lower, more preferably 55 ° C. to 80 ° C., still more preferably 60 ° C. to 80 ° C.
〔４〕精製条件
２－アセチルテトラヒドロピリジン化合物を含む反応混合物に抽出溶媒と水および中和用の塩基を添加し、反応混合物に含まれる水溶性成分と２－アセチルテトラヒドロピリジン化合物を含む非水溶性成分を液液分離する。
この抽出溶媒は水と混和しない溶媒であればよく、炭化水素系やエーテル系溶媒が好ましい、より好ましくは炭化水素系溶媒が好ましく、さらに好ましくは、ヘキサンである。
[4] Purification conditions An extraction solvent, water and a base for neutralization are added to the reaction mixture containing the 2-acetyltetrahydropyridine compound, and the water-soluble component contained in the reaction mixture and the 2-acetyltetrahydropyridine compound are water-insoluble. Liquid-liquid separation of components.
The extraction solvent may be any solvent that is immiscible with water, and is preferably a hydrocarbon-based solvent or an ether-based solvent, more preferably a hydrocarbon-based solvent, and even more preferably hexane.
水溶性成分と非水溶性成分を液液分離した後、２－アセチルテトラヒドロピリジン化合物を含む非水溶性の抽出溶媒画分を減圧留去することで、より純度の高い２－アセチルテトラヒドロピリジン化合物を得る。
得られた２－アセチルテトラヒドロピリジン化合物はこのままで使用することもできるが、香料用途の場合は、さらに精製して純度を高めることが好ましい。
具体的には、公知の蒸留設備を用いる蒸留による精製が好適である。蒸留法として、単蒸留、精留、フラッシュ蒸留、短工程蒸留などが挙げられる。
After liquid-liquid separation of the water-soluble component and the water-insoluble component, the water-insoluble extraction solvent fraction containing the 2-acetyltetrahydropyridine compound is distilled off under reduced pressure to obtain a higher-purity 2-acetyltetrahydropyridine compound. obtain.
The obtained 2-acetyltetrahydropyridine compound can be used as it is, but in the case of fragrance use, it is preferable to further purify it to increase its purity.
Specifically, purification by distillation using a known distillation facility is preferable. Examples of the distillation method include simple distillation, rectification, flash distillation, short-step distillation and the like.
蒸発温度は、収率の低下を防ぐために８０℃以下で行うが、好ましくは７０℃以下、より好ましくは４０～６０℃で留出させることが望ましい。
そのため、減圧下で蒸留する必要があるが、減圧用の装置は、真空ポンプの他に、油回転ポンプ、メカニカルブースターポンプ、拡散ポンプなどの装置を使うことができる。
The evaporation temperature is 80 ° C. or lower in order to prevent a decrease in yield, but it is preferable to distill at 70 ° C. or lower, more preferably 40 to 60 ° C.
Therefore, it is necessary to distill under reduced pressure, but as the depressurizing device, a device such as an oil rotary pump, a mechanical booster pump, or a diffusion pump can be used in addition to the vacuum pump.
蒸留時の減圧度は、８０℃以下で２－アセチルテトラヒドロピリジン化合物が留出する圧力であれば限定されないが、より低圧で蒸留することが望ましく、２０００Ｐａ以下が好ましく、１０００Ｐａ以下がより好ましく、さらに好ましくは５００Ｐａ以下である。
また、蒸留時の重合による収率低下を防ぐために、トリアセチンやトリエチルシトレートなどの溶媒で希釈して蒸留しても良いし、トコフェロールやＢＨＴなどの酸化防止剤を適宜使用しても良い。
The degree of reduced pressure during distillation is not limited as long as the pressure is such that the 2-acetyltetrahydropyridine compound is distilled at 80 ° C. or lower, but it is desirable to distill at a lower pressure, preferably 2000 Pa or less, more preferably 1000 Pa or less, and further. It is preferably 500 Pa or less.
Further, in order to prevent a decrease in yield due to polymerization during distillation, the product may be diluted with a solvent such as triacetin or triethylcitrate for distillation, or an antioxidant such as tocopherol or BHT may be appropriately used.
安価に香料原料を製造する条件として、合成反応の収率が２０％以上で、精製操作が簡単な単蒸留による精製後の純度が９０％以上になるように、有機溶媒の最適化を検討した。
ここで、以下の実施例および比較例に記載の収率は、原料１，３－ジヒドロキシアセトン（MW=90.08）に対する生成物２-アセチルテトラヒドロピリジン（MW=125.171）のモル割合を意味する。
As a condition for inexpensively producing a fragrance raw material, optimization of an organic solvent was examined so that the yield of the synthetic reaction would be 20% or more and the purity after purification by simple distillation by simple purification operation would be 90% or more. ..
Here, the yields described in the following Examples and Comparative Examples mean the molar ratio of the product 2-acetyltetrahydropyridine (MW = 125.171) to the raw material 1,3-dihydroxyacetone (MW = 90.08).
〔実施例１〕
Ｎ，Ｎ－ジメチルホルムアミド２４０．０ｇ、亜硫酸水素ナトリウム１２０．０ｇ、Ｌ－プロリン８０．０ｇ、１，３－ジヒドロキシアセトン４０．０ｇを加熱撹拌し、６０℃にて２時間反応させて反応混合物を得た。
上記反応混合物を冷却後、それに水３２０ｇ、１６％水酸化ナトリウム水溶液１３００ｇを順次加えた後、ヘキサン１３００ｇを加えて、２－アセチルテトラヒドロピリジン化合物を抽出した。
抽出物に含まれるヘキサンを減圧留去後、単蒸留による精製を行い、２－アセチルテトラヒドロピリジン化合物１３．２ｇ（収率２３．７％）を純度９９．６％で得た。
[Example 1]
240.0 g of N, N-dimethylformamide, 120.0 g of sodium bisulfite, 80.0 g of L-proline, and 40.0 g of 1,3-dihydroxyacetone were heated and stirred and reacted at 60 ° C. for 2 hours to prepare a reaction mixture. Obtained.
After cooling the reaction mixture, 320 g of water and 1300 g of a 16% aqueous sodium hydroxide solution were sequentially added, and then 1300 g of hexane was added to extract a 2-acetyltetrahydropyridine compound.
Hexane contained in the extract was distilled off under reduced pressure and then purified by simple distillation to obtain 13.2 g (yield 23.7%) of 2-acetyltetrahydropyridine compound with a purity of 99.6%.
〔実施例２〕
実施例１の反応温度を８０℃に変更した以外は、実施例１と同様の操作を行った。２－アセチルテトラヒドロピリジン化合物を２３．１ｇ（収率４１．５％）と高収率で得ることができたが、純度が９８．２％であった。
[Example 2]
The same operation as in Example 1 was performed except that the reaction temperature of Example 1 was changed to 80 ° C. The 2-acetyltetrahydropyridine compound could be obtained in a high yield of 23.1 g (yield 41.5%), but the purity was 98.2%.
〔実施例３〕
実施例１で使用したＮ，Ｎ－ジメチルホルムアミドの代わりに、エチレンカーボネートを用いて同様の操作を行った。２－アセチルテトラヒドロピリジン化合物１２．３ｇ（収率２２．１％）を純度９８．８％で得た。
[Example 3]
The same operation was carried out using ethylene carbonate instead of the N, N-dimethylformamide used in Example 1. 12.3 g (yield 22.1%) of 2-acetyltetrahydropyridine compound was obtained with a purity of 98.8%.
〔実施例４〕
実施例１で使用したＮ，Ｎ－ジメチルホルムアミドの代わりに、ジメチルスルホキシドを用いて同様の操作を行った。２－アセチルテトラヒドロピリジン化合物１４．５ｇ（収率２６．０％）を純度９９．４％で得た。
[Example 4]
The same operation was performed using dimethyl sulfoxide instead of N, N-dimethylformamide used in Example 1. 14.5 g (yield 26.0%) of 2-acetyltetrahydropyridine compound was obtained with a purity of 99.4%.
〔実施例５〕
実施例１で使用したＮ，Ｎ－ジメチルホルムアミドの代わりに、Ｎ，Ｎ－ジメチルアセトアミドを用いて同様の操作を行った。２－アセチルテトラヒドロピリジン化合物１２．０ｇ（収率２１．６％）を純度９８．６％で得た。
[Example 5]
The same operation was performed using N, N-dimethylacetamide instead of N, N-dimethylformamide used in Example 1. 12.0 g (yield 21.6%) of 2-acetyltetrahydropyridine compound was obtained with a purity of 98.6%.
〔比較例１〕
実施例１の反応温度を１００℃に変更した以外は、実施例１と同様の操作を行った。２－アセチルテトラヒドロピリジン化合物８．８ｇ（収率１５．８％）を得ることができたが、純度が３２．２％であった。
[Comparative Example 1]
The same operation as in Example 1 was performed except that the reaction temperature of Example 1 was changed to 100 ° C. 8.8 g (yield 15.8%) of the 2-acetyltetrahydropyridine compound could be obtained, but the purity was 32.2%.
〔比較例２〕
実施例１の反応温度を５０℃に変更した以外は、実施例１と同様の操作を行った。２－アセチルテトラヒドロピリジン化合物１．１ｇ（収率１．９％）と低収率であったが、純度が９９．７％であった。
[Comparative Example 2]
The same operation as in Example 1 was carried out except that the reaction temperature of Example 1 was changed to 50 ° C. The yield was as low as 1.1 g (yield 1.9%) of the 2-acetyltetrahydropyridine compound, but the purity was 99.7%.
〔比較例３〕
実施例１で使用したＮ，Ｎ－ジメチルホルムアミドの代わりに、水に変更した以外は、実施例１と同様の操作を行った。２－アセチルテトラヒドロピリジン化合物は合成できなかった。
[Comparative Example 3]
The same operation as in Example 1 was carried out except that water was used instead of N, N-dimethylformamide used in Example 1. The 2-acetyltetrahydropyridine compound could not be synthesized.
〔比較例４〕
実施例１で使用したＮ，Ｎ－ジメチルホルムアミドの代わりに、アセトニトリルに変更した以外は、実施例１と同様の操作を行った。２－アセチルテトラヒドロピリジン化合物は４．６ｇ（収率８．３％）と低収率であったが、純度が９６．６％であった。
[Comparative Example 4]
The same operation as in Example 1 was carried out except that acetonitrile was used instead of N, N-dimethylformamide used in Example 1. The 2-acetyltetrahydropyridine compound had a low yield of 4.6 g (yield 8.3%), but the purity was 96.6%.
〔比較例５〕
実施例１で使用したＮ，Ｎ－ジメチルホルムアミドの代わりにニトロメタンに変更した以外は、実施例１と同様の操作を行った。２－アセチルテトラヒドロピリジン化合物は０．７ｇ（収率１．３％）と低収率で、純度が８８．２％であった。
[Comparative Example 5]
The same operation as in Example 1 was carried out except that nitromethane was used instead of N, N-dimethylformamide used in Example 1. The 2-acetyltetrahydropyridine compound had a low yield of 0.7 g (yield 1.3%) and a purity of 88.2%.
〔比較例６〕
実施例１で使用したＮ，Ｎ－ジメチルホルムアミドの代わりに、アセトンに変更した以外は、実施例１と同様の操作を行った。２－アセチルテトラヒドロピリジン化合物は０．３ｇ（収率０．５％）と低収率で、純度が４９．５％であった。
[Comparative Example 6]
The same operation as in Example 1 was carried out except that acetone was used instead of N, N-dimethylformamide used in Example 1. The 2-acetyltetrahydropyridine compound had a low yield of 0.3 g (yield 0.5%) and a purity of 49.5%.
〔比較例７〕
実施例１で使用したＮ，Ｎ－ジメチルホルムアミドの代わりに、テトラヒドロフランに変更した以外は、実施例１と同様の操作を行った。２－アセチルテトラヒドロピリジン化合物は０．３ｇ（収率０．５％）と低収率で、純度が４０．５％であった。
[Comparative Example 7]
The same operation as in Example 1 was carried out except that the N, N-dimethylformamide used in Example 1 was changed to tetrahydrofuran. The 2-acetyltetrahydropyridine compound had a low yield of 0.3 g (yield 0.5%) and a purity of 40.5%.
〔比較例８〕
実施例１で使用したＮ，Ｎ－ジメチルホルムアミドの代わりに、酢酸エチルに変更した以外は、実施例１と同様の操作を行った。２－アセチルテトラヒドロピリジン化合物は０．５ｇ（収率０．９％）と低収率で、純度が８３．０％であった。
[Comparative Example 8]
The same operation as in Example 1 was carried out except that the N, N-dimethylformamide used in Example 1 was changed to ethyl acetate. The 2-acetyltetrahydropyridine compound had a low yield of 0.5 g (yield 0.9%) and a purity of 83.0%.
〔比較例９〕
実施例１で使用したＮ，Ｎ－ジメチルホルムアミドの代わりに、クロロホルムに変更した以外は、実施例１と同様の操作を行った。２－アセチルテトラヒドロピリジン化合物は０．９ｇ（収率１．６％）と低収率で、純度が９２．０％であった。
[Comparative Example 9]
The same operation as in Example 1 was carried out except that chloroform was used instead of N, N-dimethylformamide used in Example 1. The 2-acetyltetrahydropyridine compound had a low yield of 0.9 g (yield 1.6%) and a purity of 92.0%.
〔比較例１０〕
実施例１で使用したＮ，Ｎ－ジメチルホルムアミドの代わりに、ｔ－ブチルアルコールに変更した以外は、実施例１と同様の操作を行った。２－アセチルテトラヒドロピリジン化合物は３．３ｇ（収率５．９％）と低収率で、純度が８０．７％であった。
[Comparative Example 10]
The same operation as in Example 1 was carried out except that the N, N-dimethylformamide used in Example 1 was changed to t-butyl alcohol. The 2-acetyltetrahydropyridine compound had a low yield of 3.3 g (yield 5.9%) and a purity of 80.7%.
上記実施例１～５、比較例１～１０を表２に示す。 Table 2 shows Examples 1 to 5 and Comparative Examples 1 to 10.
ミルクフレーバー（小川香料株式会社製）に実施例１で得られた２－アセチルテトラヒドロピリジン化合物を添加し、香料組成物を作成した。その香料組成物をミルク入りコーヒーに添加したところ、乳感が向上することが確認できた。 The 2-acetyltetrahydropyridine compound obtained in Example 1 was added to a milk flavor (manufactured by Ogawa & Co., Ltd.) to prepare a fragrance composition. When the flavor composition was added to coffee containing milk, it was confirmed that the milky feeling was improved.
本発明の方法によれば、有機溶媒中でプロリン、１，３－ジヒドロキシアセトン、亜硫酸水素ナトリウムを攪拌混合した後、単蒸留することによって、高純度の２－アセチルテトラヒドロピリジン化合物を高い収率で容易に製造することができる。
特に、本発明の方法は、発火性の高い原料を使用しないので安全性に優れ、製造工数も少ないという点で経済性に極めて優れている。
According to the method of the present invention, a high-purity 2-acetyltetrahydropyridine compound is obtained in a high yield by stirring and mixing proline, 1,3-dihydroxyacetone, and sodium bisulfite in an organic solvent and then performing simple distillation. It can be easily manufactured.
In particular, the method of the present invention is excellent in safety because it does not use a highly ignitable raw material, and is extremely economical in that the manufacturing man-hours are small.
Claims (5)
（ａ）有機溶媒の常圧での沸点（Ｘ℃）と攪拌混合させる反応温度（Ｙ℃）の差（Ｘ－Ｙ）が７０℃以上２００℃以下になるように有機溶媒及び反応温度を選択すること、及び、（ｂ）攪拌混合させる反応温度を５０℃を超えて８０℃以下の範囲内で選択すること、
を特徴とし、
ここで、２－アセチルテトラヒドロピリジン化合物は、２－アセチル－３，４，５，６－テトラヒドロピリジン、２－アセチル－１，４，５，６－テトラヒドロピリジンのいずれか一方又は双方を含むこと、
を特徴とする２－アセチルテトラヒドロピリジン化合物の製造方法。 A method for producing a 2-acetyltetrahydropyridine compound by stirring and mixing proline, 1,3-dihydroxyacetone and sodium bisulfite in an organic solvent and reacting them.
(A) Select the organic solvent and reaction temperature so that the difference (XY) between the boiling point (X ° C.) of the organic solvent at normal pressure and the reaction temperature (Y ° C.) for stirring and mixing is 70 ° C. or higher and 200 ° C. or lower. And (b) select the reaction temperature to be stirred and mixed within the range of more than 50 ° C and 80 ° C or less.
Characterized by
Here, the 2-acetyltetrahydropyridine compound comprises either or both of 2-acetyl-3,4,5,6-tetrahydropyridine and 2-acetyl-1,4,5,6-tetrahydropyridine.
A method for producing a 2-acetyltetrahydropyridine compound.
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