JPH04164080A - Production of furanone derivative - Google Patents
Production of furanone derivativeInfo
- Publication number
- JPH04164080A JPH04164080A JP29007190A JP29007190A JPH04164080A JP H04164080 A JPH04164080 A JP H04164080A JP 29007190 A JP29007190 A JP 29007190A JP 29007190 A JP29007190 A JP 29007190A JP H04164080 A JPH04164080 A JP H04164080A
- Authority
- JP
- Japan
- Prior art keywords
- reaction
- reaction solution
- formula
- solvent
- compound
- 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
- 150000002241 furanones Chemical class 0.000 title claims description 13
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- 238000006243 chemical reaction Methods 0.000 claims abstract description 37
- 150000001875 compounds Chemical class 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000002904 solvent Substances 0.000 claims abstract description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 abstract description 15
- CEUSUXPNLNJGEP-UHFFFAOYSA-N 4,4-dibromo-2,5-dihydroxyhexan-3-one Chemical compound CC(O)C(=O)C(Br)(Br)C(C)O CEUSUXPNLNJGEP-UHFFFAOYSA-N 0.000 abstract description 2
- 238000004040 coloring Methods 0.000 abstract description 2
- WFIZEGIEIOHZCP-UHFFFAOYSA-M potassium formate Chemical compound [K+].[O-]C=O WFIZEGIEIOHZCP-UHFFFAOYSA-M 0.000 abstract description 2
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 20
- 239000000243 solution Substances 0.000 description 16
- 239000007864 aqueous solution Substances 0.000 description 13
- 239000000047 product Substances 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 239000012043 crude product Substances 0.000 description 7
- 239000013078 crystal Substances 0.000 description 7
- 239000000741 silica gel Substances 0.000 description 7
- 229910002027 silica gel Inorganic materials 0.000 description 7
- 229910000160 potassium phosphate Inorganic materials 0.000 description 5
- 235000011009 potassium phosphates Nutrition 0.000 description 5
- 229910000404 tripotassium phosphate Inorganic materials 0.000 description 5
- 235000019798 tripotassium phosphate Nutrition 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- TXBANKNWILQCFG-UHFFFAOYSA-N 4-hydroxyfuran-3-one Chemical compound OC1=COCC1=O TXBANKNWILQCFG-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- INAXVXBDKKUCGI-UHFFFAOYSA-N 4-hydroxy-2,5-dimethylfuran-3-one Chemical compound CC1OC(C)=C(O)C1=O INAXVXBDKKUCGI-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 229910000402 monopotassium phosphate Inorganic materials 0.000 description 2
- 235000019796 monopotassium phosphate Nutrition 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 description 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 235000011181 potassium carbonates Nutrition 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- AQJAHIKLRWQRAX-UHFFFAOYSA-N 2,5-dihydroxyhexan-3-one Chemical compound CC(O)CC(=O)C(C)O AQJAHIKLRWQRAX-UHFFFAOYSA-N 0.000 description 1
- TWRGTNSJAIAGJN-UHFFFAOYSA-N 2,5-dimethyl-2,3-dihydrofuran-4-ol Chemical compound CC1CC(O)=C(C)O1 TWRGTNSJAIAGJN-UHFFFAOYSA-N 0.000 description 1
- QQZOPKMRPOGIEB-UHFFFAOYSA-N 2-Oxohexane Chemical compound CCCCC(C)=O QQZOPKMRPOGIEB-UHFFFAOYSA-N 0.000 description 1
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical class OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- CBOCVOKPQGJKKJ-UHFFFAOYSA-L Calcium formate Chemical compound [Ca+2].[O-]C=O.[O-]C=O CBOCVOKPQGJKKJ-UHFFFAOYSA-L 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
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 239000004280 Sodium formate Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 238000005575 aldol reaction Methods 0.000 description 1
- -1 alkali metal borates Chemical class 0.000 description 1
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 1
- 150000008041 alkali metal carbonates Chemical class 0.000 description 1
- 229910000318 alkali metal phosphate Inorganic materials 0.000 description 1
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 229910000316 alkaline earth metal phosphate Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 description 1
- 239000001639 calcium acetate Substances 0.000 description 1
- 235000011092 calcium acetate Nutrition 0.000 description 1
- 229960005147 calcium acetate Drugs 0.000 description 1
- 239000004281 calcium formate Substances 0.000 description 1
- 235000019255 calcium formate Nutrition 0.000 description 1
- 229940044172 calcium formate Drugs 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- RUDATBOHQWOJDD-BSWAIDMHSA-N chenodeoxycholic acid Chemical compound C([C@H]1C[C@H]2O)[C@H](O)CC[C@]1(C)[C@@H]1[C@@H]2[C@@H]2CC[C@H]([C@@H](CCC(O)=O)C)[C@@]2(C)CC1 RUDATBOHQWOJDD-BSWAIDMHSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- DUTVPTOXFQPHKZ-UHFFFAOYSA-N hex-3-yne-1,5-diol Chemical compound CC(O)C#CCCO DUTVPTOXFQPHKZ-UHFFFAOYSA-N 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 229910000042 hydrogen bromide Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 229940008015 lithium carbonate Drugs 0.000 description 1
- HQRPHMAXFVUBJX-UHFFFAOYSA-M lithium;hydrogen carbonate Chemical compound [Li+].OC([O-])=O HQRPHMAXFVUBJX-UHFFFAOYSA-M 0.000 description 1
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 description 1
- 239000011654 magnesium acetate Substances 0.000 description 1
- 235000011285 magnesium acetate Nutrition 0.000 description 1
- 229940069446 magnesium acetate Drugs 0.000 description 1
- GMDNUWQNDQDBNQ-UHFFFAOYSA-L magnesium;diformate Chemical compound [Mg+2].[O-]C=O.[O-]C=O GMDNUWQNDQDBNQ-UHFFFAOYSA-L 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 229940093956 potassium carbonate Drugs 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 229940001593 sodium carbonate Drugs 0.000 description 1
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 description 1
- 235000019254 sodium formate Nutrition 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Landscapes
- Furan Compounds (AREA)
- Cosmetics (AREA)
Abstract
Description
【発明の詳細な説明】 産業上の利用分野 本発明は、フラノン誘導体の製造方法に関する。[Detailed description of the invention] Industrial applications The present invention relates to a method for producing furanone derivatives.
従来の技術及びその問題点
下記一般式（ｎ）
［式中Ｒは共にメチル基であるか、又は一方がメチル基
で他方がエチル基を示す。］
で表わされるフラノン誘導体は、食品用香気物質として
有用な化合物である。BACKGROUND TECHNOLOGY AND PROBLEMS THEREOF The following general formula (n) [In the formula, both R's are methyl groups, or one is a methyl group and the other is an ethyl group. ] Furanone derivatives represented by these are compounds useful as aroma substances for foods.
従来、一般式（ＩＩ）で表わされる化合物の製造方法に
関しては、種々の提案がなされて来た。例えば有機合成
化学協会主催の有機合成化学講習会テキスト第７頁（１
９８９年１１月）には、下記反応式に従い、３−ヘキシ
ン−２，６−ジオールから四工程を経て２．５−ジメチ
ル−４−ヒドロキシ−２，３−ジヒドロフランを合成す
る方法が開示されている。Conventionally, various proposals have been made regarding methods for producing the compound represented by general formula (II). For example, page 7 (1
(November 1989) disclosed a method for synthesizing 2,5-dimethyl-4-hydroxy-2,3-dihydrofuran from 3-hexyne-2,6-diol through four steps according to the following reaction formula. ing.
反応式
％式％
しかしながら、上記の方法では、第四工程の収率が約６
７％程度と低く、加えて生成物は赤褐色系統の着色が顕
著であるため、その精製に多大のエネルギーを必要とし
、それ枚目的とするフラノン誘導体（ＩＩ）が分解して
歩留まりが悪くなるのを避は得なくなる。更に上記反応
で用いられるアミン誘導体がフラノン誘導体（ｎ）に少
量残留するため香気を損ねるという欠点をも有している
。However, in the above method, the yield of the fourth step is about 6
In addition, since the product has a remarkable reddish-brown coloring, a large amount of energy is required to purify it, and the desired furanone derivative (II) decomposes, resulting in a poor yield. becomes unavoidable. Furthermore, since a small amount of the amine derivative used in the above reaction remains in the furanone derivative (n), it has the disadvantage that the aroma is impaired.
問題点を解決するための手段
本発明者らは、上記従来法の第四工程につき種々の検討
を行なった結果、生成物が低収率、低純度で得られる原
因は、副反応として下記反応式に示す逆アルドール反応
が進行していることにあるのを確認するに至った。Means for Solving the Problems The present inventors have conducted various studies on the fourth step of the above-mentioned conventional method, and have found that the reason why the product is obtained in low yield and purity is due to the following reaction as a side reaction. It was confirmed that the reverse aldol reaction shown in the formula was proceeding.
ＣＨ３ＣＨＯＣＨＢｒ２ ＋ ＣＨ３ＣＨＯ昌
アルコール系溶媒中でアミン誘導体を作用させるという
上記第四工程のような強塩基性の反応条件下では、上記
副反応は到底避は得ないものである。Under strongly basic reaction conditions such as in the fourth step of reacting an amine derivative in a CH3CHOCHBr2 + CH3CHO alcoholic solvent, the side reactions described above are completely unavoidable.
本発明者らは、斯かる現状に鑑み上記一般式（ＩＩ）で
表わされるフラノン誘導体の効率よい製造方法を開発す
べく鋭意検討を重ねた結果、ここに本発明を完成するに
至った。In view of the current situation, the present inventors have conducted extensive studies to develop an efficient method for producing the furanone derivative represented by the above general formula (II), and have now completed the present invention.
即ち、本発明は、水を溶媒とする反応液中で、一般式（
Ｉ）
［式中Ｒは前記に同じ。コ
で表わされる化合物に、塩基を作用させることを特徴と
する一般式（ＩＩ）で表わされるフラノン誘導体の製造
方法に係る。That is, the present invention provides a reaction solution containing water as a solvent, in which the general formula (
I) [In the formula, R is the same as above. The present invention relates to a method for producing a furanone derivative represented by the general formula (II), which comprises reacting a base with a compound represented by the formula (II).
本発明において、出発原料として用いられる一般式（１
）の化合物は、公知の化合物である。In the present invention, the general formula (1
) is a known compound.
本発明では、一般式（１）の化合物は、水中で臭化水素
を遊離し、一般式（ｎ）のフラノン誘導体に変換される
。本発明では、反応系内に塩基を存在させることにより
、反応系を所望のｐＨに保持しておくことができる。本
発明の反応は、ｐＴ（３〜８の範囲で良好に進行し、ｐ
Ｈ５付近で特に良好に進行する。ｐＨ８よりアルカリ側
では、相対的に反応速度は高まるが、反応選択性が低下
し、目的物の収率の低下を来たすので、好ましくない。In the present invention, the compound of general formula (1) liberates hydrogen bromide in water and is converted into the furanone derivative of general formula (n). In the present invention, the presence of a base in the reaction system allows the reaction system to be maintained at a desired pH. The reaction of the present invention proceeds well at pT (in the range of 3 to 8, and p
It progresses particularly well near H5. If the pH is more alkaline than 8, the reaction rate increases relatively, but the reaction selectivity decreases and the yield of the target product decreases, which is not preferable.
一方、ｐＨ３より酸性側では、反応速度が著しく遅くな
り、反応効率が低下するので、好ましくない。On the other hand, if the pH is more acidic than 3, the reaction rate becomes extremely slow and the reaction efficiency decreases, which is not preferable.
本発明で用いられる塩基としては、反応系を所望のｐＨ
に保持できるものである限り従来公知のものを広く使用
でき、例えば水酸化リチウム、水酸化ナトリウム、水酸
化カリウム、水酸化マグネシウム、水酸化カルシウム等
のアルカリ金属及びアルカリ土類金属の水酸化物、蟻酸
ナトリウム、蟻酸カリウム、酢酸リチウム、燦々ナトリ
ウム、酢酸カリウム、蟻酸マグネシウム、蟻酸カルシウ
ム、酢酸マグネシウム、酢酸カルシウム等のアルカリ金
属及びアルカリ土類金属の低級カルボン酸塩、炭酸リチ
ウム、炭酸ナトリウム、炭酸カリウム、重炭酸リチウム
、重炭酸ナトリウム、重炭酸カリウム等のアルカリ金属
炭酸塩もしくは重炭酸塩、アルカリ金属リン酸塩、アル
カリ土類金属リン酸塩、アルカリ金属硼酸塩、アルカリ
金属珪酸塩等が挙げられる。これら塩基の使用量として
は、一般式（１）の化合物に対して通常２〜５当量、好
ましくは２．２〜３当量とするのがよい。The base used in the present invention can be used to adjust the reaction system to a desired pH.
A wide variety of conventionally known materials can be used as long as they can be maintained at Lower carboxylates of alkali metals and alkaline earth metals such as sodium formate, potassium formate, lithium acetate, sodium sansan, potassium acetate, magnesium formate, calcium formate, magnesium acetate, calcium acetate, lithium carbonate, sodium carbonate, potassium carbonate, Examples include alkali metal carbonates or bicarbonates such as lithium bicarbonate, sodium bicarbonate, and potassium bicarbonate, alkali metal phosphates, alkaline earth metal phosphates, alkali metal borates, and alkali metal silicates. The amount of these bases to be used is usually 2 to 5 equivalents, preferably 2.2 to 3 equivalents, relative to the compound of general formula (1).
本発明における反応温度は、通常室温〜１２０℃程度、
好ましくは８０〜１００℃程度とするのがよい。The reaction temperature in the present invention is usually room temperature to about 120°C,
Preferably, the temperature is about 80 to 100°C.
実施例 以下に実施例を示して本発明をより一層明らかにする。Example Examples are shown below to further clarify the present invention.
実施例１
丸底フラスコに４，４−ジブロモ−２，５−ジヒドロキ
シ−３−へキサノン２９０ｍｇ（１，Ｏｍｍｏｌ） 、
水５ｍｌ及び酢酸２４７ｍｇ（３，Ｏｍｍｏｌ）を仕込
み、均一溶液とした。容器内を窒素置換した後、液温９
６〜９８℃で３０分反応させた。反応液のｐＨはこの間
６．４〜４．１に保持されていた。反応液を冷却して酢
酸エチルで抽出し、減圧濃縮すると、淡黄色結晶性粗生
成物が１１２ｍｇ得られた。このものはシリカゲルカラ
ムで精製すると、２，５−ジメチル−４゜５−ジヒドロ
フラン−３−オール−４−オンが白色結晶として９８．
６ｍｇ得られた（収率７７、。Example 1 290 mg (1, Ommol) of 4,4-dibromo-2,5-dihydroxy-3-hexanone in a round bottom flask,
5 ml of water and 247 mg (3,0 mmol) of acetic acid were added to form a homogeneous solution. After replacing the inside of the container with nitrogen, the liquid temperature is 9.
It was made to react at 6-98 degreeC for 30 minutes. During this period, the pH of the reaction solution was maintained at 6.4 to 4.1. The reaction solution was cooled, extracted with ethyl acetate, and concentrated under reduced pressure to obtain 112 mg of a pale yellow crystalline crude product. When this product was purified using a silica gel column, 2,5-dimethyl-4゜5-dihydrofuran-3-ol-4-one was obtained as white crystals with a yield of 98%.
6 mg was obtained (yield 77.
％）。%).
ｍｐ、７８〜８０℃
’ Ｈ−ＮＭＲ（ＣＤＣＡ’３ ）δ；１．４１ （ｄ
、２Ｈ，ＣＨ３Ｃ−０）２．２３ （ｓ、 ３Ｈ，
ＣＨ３Ｃ−０）４、 ４７ （ｑ、 ＩＨ，−ＣＨ
−０）７、 ６１ （ｓ、 ＩＨ，ＯＨ）実施例２
実施例１において、水と酢酸ナトリウムに代えてｐＨ８
，０である０、５Ｍリン酸カリウム塩水溶液（０，５Ｍ
リン酸二水素カリウム水溶液と０．５Ｍリン酸三カリウ
ム水溶液とを混合して得た）３ｍｌを用いた以外は、実
施例１と同様に反応及び処理を行なった。反応液のｐＨ
は８．０〜３．０に保持されていた。黄土色結晶性粗生
成物が１１Ｏｎ＋ｇ得られた。このものはシリカゲルカ
ラムで精製すると、２．５−ジメチル−４，５−ジヒド
ロフラン−３−オール−４−オンが白色結晶として９２
．５ｍｇ得られた（収率７２．２％）。mp, 78-80°C' H-NMR (CDCA'3) δ; 1.41 (d
, 2H, CH3C-0) 2.23 (s, 3H,
CH3C-0)4, 47 (q, IH, -CH
-0) 7, 61 (s, IH, OH) Example 2 In Example 1, instead of water and sodium acetate, pH 8
, 0, 0,5M potassium phosphate aqueous solution (0,5M
The reaction and treatment were carried out in the same manner as in Example 1, except that 3 ml of (obtained by mixing an aqueous solution of potassium dihydrogen phosphate and an aqueous 0.5M tripotassium phosphate solution) was used. pH of reaction solution
was maintained at 8.0 to 3.0. 11 On+g of ocher crystalline crude product was obtained. When this product was purified using a silica gel column, 2,5-dimethyl-4,5-dihydrofuran-3-ol-4-one was produced as white crystals at 92%
．． 5 mg was obtained (yield 72.2%).
実施例３
実施例２において、ｐＨ８，０である０、５Ｍリン酸カ
リウム塩水溶液に代えてｐＨ６，５である０、５Ｍリン
酸カリウム塩水溶液（０，５Ｍリン酸二水素カリウム水
溶液と０．５Ｍリン酸三カリウム水溶液とを混合して得
た）５ｍｌを用いた以外は、実施例２と同様に反応及び
処理を行なった。Example 3 In Example 2, instead of the 0.5M potassium phosphate aqueous solution having a pH of 8.0, a 0.5M potassium phosphate aqueous solution having a pH of 6.5 (0.5M potassium dihydrogen phosphate aqueous solution and a 0.5M potassium phosphate aqueous solution) was used. The reaction and treatment were carried out in the same manner as in Example 2, except that 5 ml of the solution (obtained by mixing with 5M aqueous tripotassium phosphate solution) was used.
反応液のｐＨは６．４〜３．３に保持されていた。The pH of the reaction solution was maintained at 6.4 to 3.3.
淡黄色結晶性粗生成物が１１４ｍｇ得られた。このもの
はシリカゲルカラムで精製すると、２．５−ジメチル−
４，５−ジヒドロフラン−３−オール−４−オンが白色
結晶として１０２．８ｍｇ得られた（収率８０．３％）
。114 mg of pale yellow crystalline crude product was obtained. When purified with a silica gel column, this product was purified using 2,5-dimethyl-
102.8 mg of 4,5-dihydrofuran-3-ol-4-one was obtained as white crystals (yield 80.3%).
.
実施例４
ｐ′Ｈ計を装着した丸底フラスコに４，４−ジブロモ−
２，５−ジヒドロキシ−３−へキサノン２９０ｍｇ （
１，０ｍｍｏｌ）及びｐＨ５，３に調製した０、５Ｍリ
ン酸カリウム水溶液５ｍｌを加え、容器内を窒素置換し
た。この混合物を９５℃に加熱し、これに０．５Ｍ水酸
化ナトリウム水溶液３、 ８ｍｌを２８分要して滴下し
ながら、反応液をｐＨ５，０に保持した。水酸化ナトリ
ウム水溶液を滴下終了後、実施例１と同様に処理した。Example 4 4,4-dibromo was added to a round bottom flask equipped with a p'H meter.
2,5-dihydroxy-3-hexanone 290mg (
1.0 mmol) and 5 ml of a 0.5 M aqueous potassium phosphate solution adjusted to pH 5.3 were added, and the inside of the container was purged with nitrogen. This mixture was heated to 95° C., and 3.8 ml of a 0.5 M aqueous sodium hydroxide solution was added dropwise thereto over 28 minutes while the reaction solution was maintained at pH 5.0. After dropping the sodium hydroxide aqueous solution, the same treatment as in Example 1 was carried out.
淡黄色結晶性粗生成物が１１４ｍｇ得られた。このもの
はシリカゲルカラムで精製すると、２，５−ジメチル−
４，５−ジヒドロフラン−３−オール−４−オンが白色
結晶として１００．５ｍｇ得られた（収率７８６５％）
。114 mg of pale yellow crystalline crude product was obtained. When purified using a silica gel column, this product was purified using 2,5-dimethyl-
100.5 mg of 4,5-dihydrofuran-3-ol-4-one was obtained as white crystals (yield 7865%).
.
実施例５
実施例４において０．５Ｍ水酸化ナトリウム水溶液の代
りに０．５Ｍ炭酸カリウム水溶液２．０ｍｌを２３分要
して滴下しながら反応液のｐＨを５．０に保持する以外
は実施例４と同様にして反応及び処理を行なった。淡黄
色結晶性粗生成物が１１７ｍｇ得られた。このものはシ
リカゲルカラムで精製すると、２．５−ジメチル−４，
５−ジヒドロフラン−３−オール−４−オンが白色結晶
として１０２．７ｍｇ得られた（収率８０６２％）。Example 5 Example 4 except that 2.0 ml of a 0.5 M potassium carbonate aqueous solution was added dropwise over a period of 23 minutes in place of the 0.5 M sodium hydroxide aqueous solution while the pH of the reaction solution was maintained at 5.0. The reaction and treatment were carried out in the same manner as in 4. 117 mg of pale yellow crystalline crude product was obtained. When purified using a silica gel column, 2,5-dimethyl-4,
102.7 mg of 5-dihydrofuran-3-ol-4-one was obtained as white crystals (yield: 8062%).
実施例６
実施例４において０．５Ｍ水酸化ナトリウム水溶液の代
りに０．５Ｍリン酸三カリウム水溶液２．４ｍｌを２５
分要して滴下しながら反応液のｐＨを５．０に保持する
以外は実施例４と同様にして反応及び処理を行なった。Example 6 In Example 4, 2.4 ml of 0.5 M tripotassium phosphate aqueous solution was added to 25 ml of 0.5 M tripotassium phosphate aqueous solution instead of 0.5 M sodium hydroxide aqueous solution.
The reaction and treatment were carried out in the same manner as in Example 4, except that the pH of the reaction solution was maintained at 5.0 while being added dropwise in portions.
淡黄色結晶性粗生成物が１１８ｍｇ得られた。このもの
はシリカゲルカラムで精製すると、２．５−ジメチル−
４，５−ジヒドロフラン−３−オール−４−オンが白色
結晶として１０８．３ｍｇ得られた（収率８４．６％）
。118 mg of pale yellow crystalline crude product was obtained. When purified with a silica gel column, this product was purified using 2,5-dimethyl-
108.3 mg of 4,5-dihydrofuran-3-ol-4-one was obtained as white crystals (yield 84.6%).
.
実施例７
実施例６において反応液の温度を８０℃に維持し、０．
５Ｍリン酸三カリウム水溶液２．１１を４０分要して滴
下しながら反応液のｐＨを５．０に保持する以外は実施
例６と同様にして反応及び処理を行なった。淡黄色油状
粗生成物が１２９ｍｇ得られた。このものはシリカゲル
カラムで精製すると、２．５−ジメチル−４，５−ジヒ
ドロフラン−３−オール−４−オンが白色結晶として９
４．０ｍｇ得られた（収率７３．４％）。また出発原料
である４、４−ジブロモ−２，５−ジヒドロキシ−３−
ヘキサノンが２１゜５ｍｇ回収された（回収率７．４％
）。Example 7 In Example 6, the temperature of the reaction solution was maintained at 80°C, and the temperature of the reaction solution was maintained at 80°C.
The reaction and treatment were carried out in the same manner as in Example 6, except that the pH of the reaction solution was maintained at 5.0 while dropping 2.11 parts of a 5M tripotassium phosphate aqueous solution over 40 minutes. 129 mg of pale yellow oily crude product was obtained. When this product was purified using a silica gel column, 2,5-dimethyl-4,5-dihydrofuran-3-ol-4-one was obtained as white crystals.
4.0 mg was obtained (yield 73.4%). In addition, the starting material 4,4-dibromo-2,5-dihydroxy-3-
21.5 mg of hexanone was recovered (recovery rate 7.4%).
).
発明の効果
本発明によれば、一般式（Ｉ）の化合物から一般式（Ｉ
Ｉ）のフラノン誘導体が収率よく製造され得る。また本
発明の方法に従えば、反応を水中で行なうことができる
ために、後処理が容易であるし、また生成物は着色度が
小さく高純度であるので精製も簡単であり、更に生成物
であるフラノン誘導体（ＩＩ）の香気を損なうこともな
い。Effects of the Invention According to the present invention, the compound of general formula (I) can be synthesized from the compound of general formula (I).
The furanone derivative of I) can be produced with good yield. Furthermore, according to the method of the present invention, the reaction can be carried out in water, so post-treatment is easy, and the product has a low degree of coloration and is highly pure, so purification is easy. The aroma of the furanone derivative (II) is not impaired.
（以 上）(that's all)
Claims (3)
で他方がエチル基を示す。］ で表わされる化合物に、塩基を作用させることを特徴と
する一般式 ▲数式、化学式、表等があります▼ ［式中Ｒは前記に同じ。］ で表わされるフラノン誘導体の製造方法。(1) In a reaction solution using water as a solvent, there are general formulas ▲ mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, both R's are methyl groups, or one is a methyl group and the other is an ethyl group. ] General formulas characterized by the action of a base on the compound represented by ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, R is the same as above. ] A method for producing a furanone derivative represented by:
ある請求項１記載の方法。(2) The method according to claim 1, wherein the pH of the reaction solution using water as a solvent is in the range of 3 to 8.
記載の方法。(3) Claim 1, wherein the pH of the reaction solution using water as a solvent is 5.
Method described.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2290071A JP3005693B2 (en) | 1990-10-25 | 1990-10-25 | Method for producing furanone derivative |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2290071A JP3005693B2 (en) | 1990-10-25 | 1990-10-25 | Method for producing furanone derivative |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04164080A true JPH04164080A (en) | 1992-06-09 |
| JP3005693B2 JP3005693B2 (en) | 2000-01-31 |
Family
ID=17751416
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2290071A Expired - Fee Related JP3005693B2 (en) | 1990-10-25 | 1990-10-25 | Method for producing furanone derivative |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3005693B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6108151B2 (en) * | 2012-08-31 | 2017-04-05 | 有限会社 和田機械 | Food raw material back machine |
-
1990
- 1990-10-25 JP JP2290071A patent/JP3005693B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JP3005693B2 (en) | 2000-01-31 |
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