JPH062759B2 - Method for producing furfuryl alcohol - Google Patents
Method for producing furfuryl alcoholInfo
- Publication number
- JPH062759B2 JPH062759B2 JP12292586A JP12292586A JPH062759B2 JP H062759 B2 JPH062759 B2 JP H062759B2 JP 12292586 A JP12292586 A JP 12292586A JP 12292586 A JP12292586 A JP 12292586A JP H062759 B2 JPH062759 B2 JP H062759B2
- Authority
- JP
- Japan
- Prior art keywords
- reaction
- furfuryl alcohol
- water
- allyl
- furfuryl alcohols
- 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.)
- Expired - Lifetime
Links
Description
【発明の詳細な説明】 <産業上の利用分野> 本発明は一般式(I) (式中、Rは水素原子またはメチル基を示す) で示されるフルフリルアルコール類の製造方法に関す
る。DETAILED DESCRIPTION OF THE INVENTION <Industrial field of application> The present invention has the general formula (I) (In the formula, R represents a hydrogen atom or a methyl group.) The present invention relates to a method for producing furfuryl alcohols.
<従来の技術> 上記一般式(I)で示されるフルフリルアルコール類は、
農薬,医薬,香料等の有用な中間体となるものである。<Prior Art> Furfuryl alcohols represented by the general formula (I) are
It is a useful intermediate for agricultural chemicals, pharmaceuticals, and fragrances.
従来より、カルボニル化合物とアリルハライドとの反応
によりアルコールを得る方法としては、たとえばTetra.
Let.,26 1449〜1452(1985)に示されるように、テト
ラヒドロフラン一飽和塩化アンモニウム水溶液混合溶媒
中、亜鉛存在下にカルボニル化合物とアリルハライドを
反応させる方法が知られている。Conventionally, as a method of obtaining an alcohol by the reaction of a carbonyl compound and an allyl halide, for example, Tetra.
As shown in Let., 26 1449-1452 (1985), a method is known in which a carbonyl compound is reacted with an allyl halide in the presence of zinc in a tetrahydrofuran monosaturated ammonium chloride aqueous solution mixed solvent.
しかし、この方法をフルフラールもしくは5−メチルフ
ルフラールとアリルハライドとの反応に適用した場合に
は多量のタール状物が生成し、目的とするフルフリルア
ルコール類の収率が30%以下と非常に低いなど、フル
フリルアルコール類の工業的製法としては極めて不満足
なものである。However, when this method is applied to the reaction of furfural or 5-methylfurfural with allyl halide, a large amount of tar-like product is produced, and the yield of the desired furfuryl alcohols is very low at 30% or less. Etc. are extremely unsatisfactory as an industrial method for producing furfuryl alcohols.
<発明が解決しようとする問題点> このようなことから、本発明らは上記欠点を改良し、工
業的有利に上記一般式(I)で示されるフルフリルアルコ
ール類を製造すべく種々検討の結果、フルフラール類と
アリルハライドとを特定条件下に反応させることにより
短時間で、好収率でフルフリルアルコール類が得られる
ことを見出し、本発明に至った。<Problems to be Solved by the Invention> From the above, the present inventors have made various studies to improve the above-mentioned drawbacks and industrially advantageously produce the furfuryl alcohols represented by the general formula (I). As a result, they have found that furfuryl alcohols can be obtained in a good yield in a short time by reacting furfural with an allyl halide under specific conditions, and the present invention has been completed.
<問題点を解決するための手段> すなわち本発明は、一般式(II) (式中、Rは水素原子またはメチル基を示す) で示されるフルフラール類とアリルハライドを、亜鉛お
よびアンモニウム塩の共存下、水溶媒中で反応させるこ
とを特徴とする前記一般式(I)で示されるフルフリルア
ルコール類の製造方法を提供するものである。<Means for Solving Problems> That is, the present invention provides a compound represented by the general formula (II) (Wherein R represents a hydrogen atom or a methyl group) and the allyl halide represented by the formula (I) are reacted in the presence of zinc and ammonium salts in a water solvent. A method for producing the indicated furfuryl alcohols is provided.
本発明における原料フルフラール類としてはフルフラー
ルもしくは5−メチルフルフラールが使用され、また、
アリルハライドとしてはアリルクロライド、アリルブロ
マイドが使用される。Furfural or 5-methylfurfural is used as the raw material furfural in the present invention.
As allyl halide, allyl chloride and allyl bromide are used.
この反応において、アリルハライドおよび亜鉛の使用量
は原料フルフラール類に対してそれぞれ1〜2倍モルの
範囲であることが好ましい。In this reaction, the amounts of allyl halide and zinc used are preferably in the range of 1 to 2 times the moles of the raw furfural.
反応は水溶媒中で行なわれる。溶媒としての水の使用量
は通常原料フルフラール類に対して1〜50倍重量であ
るが、特に制限されるものではない。The reaction is carried out in a water solvent. The amount of water used as a solvent is usually 1 to 50 times the weight of the raw material furfural, but is not particularly limited.
また、この反応において共存するアンモニウム塩として
は塩化アンモニウム、臭化アンモニウムなどの無機塩が
一般的であり、その使用量は反応溶媒である水に対して
通常0.05〜1倍重量である。もちろん、1倍重量を越え
ても反応は進行するが、スラリー濃度が増加し、工業的
には不利となる。また、0.05倍重量未満でも反応は進行
するが、反応の終了に長時間を必要とし、工業的には不
利となる。As the ammonium salt coexisting in this reaction, an inorganic salt such as ammonium chloride or ammonium bromide is generally used, and the amount thereof is usually 0.05 to 1 times the weight of water as a reaction solvent. Of course, the reaction proceeds even if the weight exceeds 1 time, but the slurry concentration increases, which is industrially disadvantageous. Although the reaction proceeds even if the amount is less than 0.05 times the weight, it takes a long time to complete the reaction, which is industrially disadvantageous.
反応温度は一般には0〜100℃の範囲で選ばれるが、好
ましくは5〜80℃である。The reaction temperature is generally selected in the range of 0 to 100 ° C, preferably 5 to 80 ° C.
反応の進行は機器分析たとえばガスクロマトグラフィー
により追跡され、原料フルフラール類が全部消失したと
ころで反応は終了する。反応液からのフルフリルアルコ
ール類の取り出しは、たとえば分液の後、有機層を蒸留
することにより行なわれる。The progress of the reaction is monitored by instrumental analysis such as gas chromatography, and the reaction ends when all the raw material furfurals have disappeared. The furfuryl alcohols are taken out from the reaction solution, for example, by separating the organic layer and then distilling the organic layer.
<発明の効果> かくして、本発明の方法によれば工業的容易に、短時間
で、良好な収率で目的とする前記一般式(I)で示される
フルフリルアルコール類を得ることができる。<Effects of the Invention> Thus, according to the method of the present invention, the desired furfuryl alcohols represented by the general formula (I) can be industrially easily obtained in a short time in a good yield.
<実施例> 以下、実施例により本発明を説明する。<Example> Hereinafter, the present invention will be described with reference to Examples.
実施例1 フラスコに5−メチルフルフラール44g、アリルクロ
ライド36.7g、亜鉛粉31.4gおよび水440gを仕込ん
だ後、撹拌下に35±8℃に維持しながら塩化アンモニ
ウム95gおよび水345gからなる塩化アンモニウム
水溶液を1時間を要して滴下した。滴下終了後、同温度
で2時間、保持した。Example 1 A flask was charged with 44 g of 5-methylfurfural, 36.7 g of allyl chloride, 31.4 g of zinc powder and 440 g of water, and then an aqueous ammonium chloride solution consisting of 95 g of ammonium chloride and 345 g of water while maintaining at 35 ± 8 ° C. with stirring. Was added dropwise over 1 hour. After the dropping was completed, the temperature was maintained for 2 hours at the same temperature.
反応終了後、反応液を分液し、有機層を減圧下に精留し
て2−(1−ヒドロキシ−3−ブテニル)−5−メチル
フランの留分46.6g(含量99.8%)を得た(収率76.0
%)。After the reaction was completed, the reaction solution was separated, and the organic layer was rectified under reduced pressure to obtain 46.6 g (content 99.8%) of 2- (1-hydroxy-3-butenyl) -5-methylfuran fraction. (Yield 76.0
%).
実施例 5−メチルフルフラールの代わりに等モル量のフルフラ
ールを使用する以外は実施例1と同様の反応および後処
理を行い、2−(1−ヒドロキシ−3−ブテニル)−フ
ランの留分40.2g(含量99.0%)を得た(収率72.0
%)。Example 5 The same reaction and post-treatment as in Example 1 were carried out except that an equimolar amount of furfural was used instead of 5-methylfurfural, and the fraction of 2- (1-hydroxy-3-butenyl) -furan was 40.2 g. (Content 99.0%) was obtained (yield 72.0
%).
実施例3 フラスコに5−メチルフルフラール44g、亜鉛粉3
1.4gおよび水440gを仕込んだ後、撹拌下に20
±3℃に維持しながら、臭化アンモニウム40gおよび
水400gからなる臭化アンモニウム水溶液とアリルブ
ロマイド58.1gを2時間を要して併行に滴下した。滴下
終了後、同温度で2時間、保持した。以後、実施例1と
同様の後処理を行い、2−(1−ヒドロキシ−3−ブテ
ニル)−5−メチルフランの留分45.4g(含量99.1%)
を得た(収率73.9%)。Example 3 4-methylfurfural 44 g, zinc powder 3 in a flask
After charging 1.4 g and 440 g of water, 20
While maintaining the temperature at ± 3 ° C, an aqueous ammonium bromide solution consisting of 40 g of ammonium bromide and 400 g of water and 58.1 g of allyl bromide were added dropwise in parallel over 2 hours. After the dropping was completed, the temperature was maintained for 2 hours at the same temperature. Thereafter, the same post-treatment as in Example 1 was carried out, and the fraction of 2- (1-hydroxy-3-butenyl) -5-methylfuran was 45.4 g (content 99.1%).
Was obtained (yield 73.9%).
比較例1 フラスコに5−メチルフルフラール44.0g、亜鉛粉31.4
g、塩化アンモニウム97.1g、水342.9おgおよびテト
ラヒドロフラン88.0gを仕込んだ後、撹拌下に25±3
℃に維持しながら、アリルクロライド36.7gを1時間を
要して滴下終了後、同温度で2時間、保持した。Comparative Example 1 44.0 g of 5-methylfurfural and 31.4 of zinc powder were placed in a flask.
g, ammonium chloride 97.1 g, water 342.9 g and tetrahydrofuran 88.0 g, and then 25 ± 3 with stirring
While maintaining the temperature at 0 ° C., 36.7 g of allyl chloride was added for 1 hour, and after the dropping was completed, the temperature was maintained at the same temperature for 2 hours.
反応終了後、反応液を分液し、有機層を減圧下に精留し
て、2−(1−ヒドロキシ−3−ブテニル)−5−メチ
ルフランの留分14.8g(含量98.7%)を得た(収24.0
%)。After the reaction was completed, the reaction solution was separated and the organic layer was rectified under reduced pressure to obtain 14.8 g (content 98.7%) of 2- (1-hydroxy-3-butenyl) -5-methylfuran fraction. (Sales 24.0
%).
Claims (1)
よびアンモニウム塩の共存下、水溶媒中で反応させるこ
とを特徴とする一般式 (式中、Rは前記と同じ意味を有する) で示されるフルフリルアルコール類の製造方法1. A general formula (Wherein R represents a hydrogen atom or a methyl group) and the allyl halide are reacted in the presence of zinc and ammonium salts in a water solvent. (In the formula, R has the same meaning as described above.) A method for producing furfuryl alcohols
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP12292586A JPH062759B2 (en) | 1986-05-28 | 1986-05-28 | Method for producing furfuryl alcohol |
KR1019870005238A KR940003295B1 (en) | 1986-05-28 | 1987-05-26 | Method for producing furfuryl alcohols |
DE8787107699T DE3764316D1 (en) | 1986-05-28 | 1987-05-26 | METHOD FOR PRODUCING FURFURYL ALCOHOLS. |
US07/053,687 US5008410A (en) | 1986-05-28 | 1987-05-26 | Method for producing furfuryl alcohols |
EP87107699A EP0247589B1 (en) | 1986-05-28 | 1987-05-26 | A method for producing furfuryl alcohols |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP12292586A JPH062759B2 (en) | 1986-05-28 | 1986-05-28 | Method for producing furfuryl alcohol |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS62281874A JPS62281874A (en) | 1987-12-07 |
JPH062759B2 true JPH062759B2 (en) | 1994-01-12 |
Family
ID=14848001
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP12292586A Expired - Lifetime JPH062759B2 (en) | 1986-05-28 | 1986-05-28 | Method for producing furfuryl alcohol |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH062759B2 (en) |
-
1986
- 1986-05-28 JP JP12292586A patent/JPH062759B2/en not_active Expired - Lifetime
Also Published As
Publication number | Publication date |
---|---|
JPS62281874A (en) | 1987-12-07 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP0247589B1 (en) | A method for producing furfuryl alcohols | |
JPH0332548B2 (en) | ||
JPH0713067B2 (en) | Method for producing furfuryl alcohol | |
JPS5823392B2 (en) | Method for producing N-alkyl-N-chlorothiocarbamoyl chloride | |
JPH062759B2 (en) | Method for producing furfuryl alcohol | |
JPH0311083A (en) | Silylating agent | |
DE2259222A1 (en) | NEW, 1,1-DIOXOTHIAZOLIDIN-4-ONE AND THE METHOD FOR THE PREPARATION | |
JPH062760B2 (en) | Method for producing furfuryl alcohol | |
JPH0713065B2 (en) | Method for producing furfuryl alcohol | |
JPH07110863B2 (en) | Process for producing 1-methyl-3,5,7-triaza-1-azoniatricyclodecane halide | |
EP0170517B1 (en) | Process for the production of 1,2-amino alcohols | |
JP2653138B2 (en) | Haloallylfuran carbinols and their preparation | |
JPH0713068B2 (en) | Method for producing furfuryl alcohol | |
JPH0713066B2 (en) | Method for producing furfuryl alcohol | |
JPS5840939B2 (en) | Method for producing cyclohexanedione derivatives | |
US4500733A (en) | Process for preparing dihalovinylcyclopropanecarboxylic acids | |
JPH0674224B2 (en) | Method for producing alcohols | |
JP2864985B2 (en) | Method for producing tri (secondary alkyl) silane compound | |
JPS5838268A (en) | Preparation of uracil | |
JP3839176B2 (en) | Method for producing alkali metal cyclopentadienylide and method for producing dihalobis (η-substituted cyclopentadienyl) zirconium using alkali metal cyclopentadienylide | |
EP0065356B1 (en) | A method for purification of cyclopentenolones | |
JPH0674225B2 (en) | Method for producing alcohols | |
CA1265143A (en) | Process for preparing 3-(pyrid-4-yl)propanoic acid derivatives | |
JPS5858335B2 (en) | Alpha - Chikanacetone no Seizouhou | |
JP4008306B2 (en) | Production method of terminal alkyne |