KR100526044B1 - New process for preparing alpha alkyl perfuryl alcohol - Google Patents
New process for preparing alpha alkyl perfuryl alcohol Download PDFInfo
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- KR100526044B1 KR100526044B1 KR10-1998-0034209A KR19980034209A KR100526044B1 KR 100526044 B1 KR100526044 B1 KR 100526044B1 KR 19980034209 A KR19980034209 A KR 19980034209A KR 100526044 B1 KR100526044 B1 KR 100526044B1
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- C—CHEMISTRY; METALLURGY
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- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
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Abstract
본 발명은 알파 알킬 퍼퓨릴 알콜의 신규한 제조방법에 관한 것으로, 그리너드 시약의 제조시에 마그네슘과 알킬할라이드의 반응용매로서 테트라하이드로퓨란과 방향족 하이드로카본을 1:0.5 내지 1:2의 비율로 혼합한 혼합물을 마그네슘 1몰에 대하여 120 내지 1000㎖ 사용하여 그리너드 시약을 제조한 후 화학식 1의 퍼퓨랄을 첨가하여 그리너드 반응을 완료하고, 가수분해함으로써 순도 및 수율 95% 이상의 화학식 2의 알파 알킬퍼퓨릴 알콜을 수득할 수 있고, 수득된 고순도의 알파 알킬 퍼퓨릴 알콜은 식품 등에 첨가하는 향강화제 혹은 농약, 의약 등의 중간체로 유용하게 사용된다.The present invention relates to a novel process for preparing alpha alkyl perfuryl alcohol, wherein tetrahydrofuran and aromatic hydrocarbons are used in a ratio of 1: 0.5 to 1: 2 as a reaction solvent of magnesium and alkyl halides in the preparation of the greenard reagent. The mixture was prepared using 120 to 1000 ml of magnesium per mole to prepare a Grignard reagent, and then the perfural of Formula 1 was added to complete the Grignard reaction. Alkylperfuryl alcohol can be obtained, and the high-purity alpha alkyl perfuryl alcohol obtained is usefully used as a flavoring agent added to foods or the like or as an intermediate of agrochemicals and medicines.
화학식 1Formula 1
화학식 2Formula 2
R1은 메틸, 에틸, R2는 수소, 메틸 또는 에틸그룹이다.R 1 is methyl, ethyl and R 2 is hydrogen, methyl or ethyl group.
Description
본 발명은 식품 등에 첨가되는 향강화제 및 농약, 의약 등의 중간체로 사용되는 알파 알킬 퍼퓨릴 알콜(alpha alkyl furfuryl alcohol)의 제조방법에 관한 것으로, 보다 상세하게는 테트라하이드로퓨란과 방향족 하이드로카본의 혼합물을 용매로 사용하여 알킬클로라이드 혹은 알킬브로마이드와 마그네슘으로 그리너드 시약(RMgX ;Grignard reagent)을 제조한 후 퍼퓨랄을 첨가하여 그리너드 반응과 가수분해 반응을 수행하는 알파 알킬 퍼퓨릴 알콜의 신규한 제조방법에 관한 것이다.The present invention relates to a method for preparing alpha alkyl furfuryl alcohol, which is used as an adjuvant to be added to food, etc., and intermediates such as pesticides and medicines, and more particularly, a mixture of tetrahydrofuran and an aromatic hydrocarbon. Is prepared as a solvent to prepare a Grignard reagent (RMgX; Grignard reagent) from alkyl chloride or alkyl bromide and magnesium, and then a new preparation of alpha alkyl perfuryl alcohol which is subjected to greenery reaction and hydrolysis reaction by adding perfural. It is about a method.
공지된 알킬 알파 퍼퓨릴 알콜의 제조방법으로, 미합중국 특허 4,536,349호에는 메틸아이오다인(MeI)과 마그네슘을 무수 에틸에테르의 반응용매하에서 반응시켜 그리너드시약을 제조한 후, 여기에 퍼퓨랄을 첨가해 그리너드 반응을 완결시키고, 완결된 그리너드 반응물을 암모늄 클로라이드 수용액으로 가수분해 한 후 유기층을 분리하여 에틸에테르를 제거한 잔여물을 쇼트-칼럼(Shot column)장치에서 0.5mmHg로 감압증류하여 순도 90%의 알파 메틸 퍼퓨릴 알콜을 제조하는 방법이 개시되어 있다. As a known method for preparing alkyl alpha perfuryl alcohol, U.S. Patent No. 4,536,349 discloses a greener reagent by reacting methyliodine (MeI) with magnesium in a reaction solvent of anhydrous ethyl ether, and then furfural is added thereto. After completion of the Grignard reaction, the complete Grignard reaction was hydrolyzed with an aqueous solution of ammonium chloride, the organic layer was separated, and the residue from which ethyl ether was removed was distilled under reduced pressure to 0.5mmHg in a shot column apparatus for purity. A process for preparing 90% alpha methyl perfuryl alcohol is disclosed.
그러나, 상기 특허에 의한 제조방법은 그리너드시약의 제조 및 반응에 용매로 사용되는 고가의 무수 에틸에테르의 양이 마그네슘 1몰당 1ℓ 이상으로 사용되어야 하기 때문에 경제적인 측면에서 바람직하지 못할 뿐만 아니라, 제조된 알파 메틸 퍼퓨릴 알콜의 순도가 낮아 상업화하는 경우 생산성 측면에서도 만족스러운 결과를 가져오지는 못하였다.However, the manufacturing method according to the above patent is not only economically unfavorable because the amount of expensive anhydrous ethyl ether used as a solvent in the preparation and reaction of the Greennard reagent should be used in an amount of 1 L or more per 1 mol of magnesium. The low purity of the prepared alpha methyl perfuryl alcohol did not produce satisfactory results in commercialization.
다른 방법으로, 미합중국 특허 5,358,670호에는 디에틸렌글리콜디부틸에테르(Diethylene glycol dibutyl ether)의 반응용매하에서 마그네슘과 메틸클로라이드 혹은 에틸브로마이드와 같은 알킬 할라이드(alkyl halid)를 반응시켜 그리너드 시약을 제조하는 방법이 개시되어 있다.Alternatively, U. S. Patent No. 5,358, 670 discloses a method for preparing Grignard reagents by reacting alkyl halids such as magnesium chloride or methyl chloride or ethyl bromide under a reaction solvent of diethylene glycol dibutyl ether. Is disclosed.
그러나, 제조된 그리너드 시약 반응 혼합물에 앞선 특허방법에서와 같이 퍼퓨랄을 첨가하여 알파 알킬 퍼퓨릴 알콜을 제조하는 경우 그 수득율은 60% 이하로 역시 생산성 측면에서 개선점을 찾을 수는 없었다.However, when the alpha alkyl perfuryl alcohol was prepared by adding perfural to the prepared Grignard reagent reaction mixture as in the previous patent method, the yield was not more than 60%, and there was no improvement in productivity.
본 발명의 목적은 상기와 같은 문제점을 해결하기 위하여 제안된 것으로, 그리너드시약과 퍼퓨랄을 이용하여 수율 95% 이상, 순도 95% 이상의 고수율, 고순도의 알파 알킬 퍼퓨릴 알콜을 수득할 수 있는 신규한 제조방법을 제공하는 것이다.An object of the present invention has been proposed to solve the above problems, by using the Greennard reagent and perfural to obtain a yield of 95% or more, high yield of 95% or higher, high purity alpha alkyl perfuryl alcohol It is to provide a novel manufacturing method.
즉, 본 발명은 테트라하이드로퓨란과 방향족 하이드로카본을 혼합한 혼합물을 반응용매로 사용하여 마그네슘과 알킬할라이드로 그리너드 시약을 제조한 후 퍼퓨랄을 첨가하여 그리너드 반응을 완결하고, 가수분해하여 수율 95%, 순도 95% 이상의 알파 알킬 퍼퓨릴 알콜을 제조하는 방법에 관한 것이다.That is, the present invention uses a mixture of tetrahydrofuran and an aromatic hydrocarbon as a reaction solvent to prepare a Grignard reagent with magnesium and an alkyl halide, and then add perfural to complete the Grignard reaction, followed by hydrolysis to yield. A method for preparing alpha alkyl perfuryl alcohol having a purity of 95% and higher than 95%.
이하, 본 발명을 더욱 상세히 설명하면 다음과 같다.Hereinafter, the present invention will be described in more detail.
본 발명의 알파 알킬 퍼퓨릴 알콜의 제조방법은 크게 두 단계로 나누어 볼 수 있는데, 먼저 그리너드 시약을 제조하는 단계와, 다음으로 제조된 그리너드 시약에 퍼퓨랄을 주입하여 알파 알킬 퍼퓨릴 알콜을 제조하는 단계로 이루어진다.The preparation method of the alpha alkyl perfuryl alcohol of the present invention can be broadly divided into two steps. First, a step of preparing a Grignard reagent and a second injection of perfural into the prepared Grignard reagent are used to prepare the alpha alkyl perfuryl alcohol. It is made of a manufacturing step.
본 발명에서 그리너드 시약의 제조반응은, 반응기 내부 용매내에 고체상태로 존재하는 마그네슘을 개시제로 활성화시킨 후 가스나 액체상태의 알킬클로라이드나 알킬브로마이드와 같은 알킬 할라이드를 서서히 주입하면서 개시된다. 반응초기에, 알킬클로라이드 혹은 알킬브로마이드와 용매에 용해된 활성화 마그네슘이 반응하여 알킬마그네슘클로라이드나, 알킬마그네슘브로마이드가 생성된다.In the present invention, the preparation of the Greenard reagent is initiated by activating magnesium, which is present in a solid state in a solvent inside the reactor, as an initiator and then slowly injecting an alkyl halide such as alkyl chloride or alkyl bromide in gas or liquid state. At the beginning of the reaction, alkyl chloride or alkyl bromide and activated magnesium dissolved in a solvent react to form alkylmagnesium chloride or alkylmagnesium bromide.
생성된 알킬마그네슘클로라이드나 알킬마그네슘브로마이드는 미반응 마그네슘을 다시 활성화시키고, 활성화 마그네슘이 반응용매에 용해되어 반응이 계속적으로 진행된다.The produced alkylmagnesium chloride or alkylmagnesium bromide reactivates unreacted magnesium, and the activated magnesium dissolves in the reaction solvent and the reaction proceeds continuously.
이때, 주의할 사항은 사용되는 반응용매가 활성화된 마그네슘과 생성된 그리너드 시약을 충분히 용해시켜야 한다는 것이다. 이는 반응중 생성된 그리너드 시약이 반응용매에 과포화되어 활성화 마그네슘이 용해되지 않으면, 결국 반응이 더 이상 진행하지 않게 되기 때문이다. 따라서, 그리너드 시약 제조 반응성은 용매에 대한 마그네슘, 생성되는 그리너드 시약의 용해도와 밀접한 관련이 있음을 알 수 있다.It is important to note that the reaction solvent used must dissolve the activated magnesium and the Grignard reagent. This is because if the Grignard reagent generated during the reaction is supersaturated in the reaction solvent and the activated magnesium is not dissolved, the reaction will not proceed any further. Thus, it can be seen that the Greennard reagent preparation reactivity is closely related to the solubility of magnesium in the solvent, the Greenwich reagent produced.
본 발명에서 그리너드 시약 제조시에 반응용매로는 테트라하이드로퓨란(THF)과 자일렌, 톨루엔, 벤젠 등으로 부터 선택되는 방향족 하이드로카본의 혼합물이 사용되는데, 혼합비율은 1:0.5 내지 1:2가 바람직하고, 더욱 바람직하게는 1:0.8 내지 1:1인바, 이는 활성화된 마그네슘과 생성된 그리너드 시약을 충분히 용해시키기 위함이다.In the present invention, a mixture of tetrahydrofuran (THF) and an aromatic hydrocarbon selected from xylene, toluene, benzene and the like is used as a reaction solvent in the preparation of the Greennard reagent. The mixing ratio is 1: 0.5 to 1: 2. Is preferred, and more preferably 1: 0.8 to 1: 1, in order to sufficiently dissolve the activated magnesium and the resultant Greennard reagent.
반응용매의 사용량은 테트라하이드로퓨란과 방향족 하이드로카본의 혼합비율에 따라 달라지지만 마그네슘 1몰에 대한 양으로 정의된다. 즉, 두 성분의 비율이 1:2인 경우 사용량은 마그네슘 1몰에 대하여 1000㎖이상 사용하는 것이 바람직하고, 1:0.8 내지 1:1인 경우에는 148 내지 500㎖의 소량으로 사용할 수 있고, 1:0.5인 경우에는 120 내지 145㎖를 사용하여 그리너드 시약 제조반응을 완결시킬 수 있다.The amount of the reaction solvent used depends on the mixing ratio of tetrahydrofuran and aromatic hydrocarbon, but is defined as the amount for 1 mol of magnesium. That is, when the ratio of two components is 1: 2, the amount of use is preferably 1000 ml or more per 1 mole of magnesium, and in the case of 1: 0.8 to 1: 1, a small amount of 148 to 500 ml may be used. In the case of 0.5, 120 to 145 ml may be used to complete the Greennard reagent preparation reaction.
따라서, 테트라하이드로퓨란과 방향족 하이드로카본의 혼합비율이 1:0.5 내지 1:2, 바람직하게는 1:0.8 내지 1:1이므로, 사용량의 범위는 120 내지 1,000㎖, 바람직하게는 148 내지 500㎖가 된다. Therefore, since the mixing ratio of tetrahydrofuran and aromatic hydrocarbon is 1: 0.5 to 1: 2, preferably 1: 0.8 to 1: 1, the usage range is 120 to 1,000 ml, preferably 148 to 500 ml. do.
본 발명의 그리너드 제조반응에서 개시제로는 아이오다인(I2), 디브로모에탄(Dibromoethane), 알킬마그네슘할라이드가 사용될 수 있고, 사용량은 마그네슘 사용 몰수에 대하여 1몰%가 바람직하다.Iodine (I 2 ), dibromoethane, alkylmagnesium halide may be used as an initiator in the greennard production reaction of the present invention, and the amount of use is preferably 1 mol% based on the number of moles of magnesium used.
마그네슘을 개시제로 활성화시킨 후 가스나 액체상태의 알킬클로라이드 또는 알킬브로마이드와 같은 알킬할라이드를 마그네슘 1몰에 대하여 1.05 내지 1.20몰로 첨가하여 반응온도는 0 내지 80℃를 유지하면서 반응을 진행하는데, 반응온도가 0℃ 미만인 경우에는 활성화된 마그네슘과 알킬마그네슘할라이드가 침전되어 반응성이 현저히 저하되고, 80℃를 초과하는 경우에는 타르형태의 부산물이 생성되어 바람직하지 못하다.After activating magnesium as an initiator, an alkyl halide such as alkyl chloride or alkyl bromide in gas or liquid state is added at 1.05 to 1.20 moles with respect to 1 mole of magnesium, and the reaction temperature is maintained at 0 to 80 ° C. When it is less than 0 ℃ activated magnesium and alkyl magnesium halide precipitates remarkably decrease the reactivity, when it exceeds 80 ℃ it is not desirable to produce a by-product of the tar form.
다음으로 제조된 그리너드 시약에 하기 화학식 1의 퍼퓨랄을 주입하여 그리너드 반응을 완결시키는데, 이때 퍼퓨랄의 함량은 통상 사용되는 양의 범위내에서 첨가될 수 있으나, 바람직하게는 마그네슘 1몰에 대하여 0.96몰을 사용하여, 부산물의 생성을 최소화하기 위하여 60℃ 이하에서 반응을 완결시킨다.Next, inject the perfural of Formula 1 to the prepared Grignard reagent to complete the Grignard reaction, wherein the content of perfural may be added within the range of conventionally used amount, preferably in 1 mol of magnesium. Using 0.96 moles per mole, the reaction is completed below 60 ° C. to minimize the production of by-products.
[화학식 1][Formula 1]
여기서, R2는 수소, 메틸 또는 에틸그룹이다.Wherein R 2 is hydrogen, methyl or ethyl group.
그리너드 반응완결후 가수분해 반응은 염산, 황산, 초산, 암모늄클로라이드 수용액을 이용하여 1 내지 100℃의 범위내에서 다양한 조건으로 진행하는 것이 허용된다.After completion of the Greennard reaction, the hydrolysis reaction is allowed to proceed under various conditions within the range of 1 to 100 ° C using aqueous hydrochloric acid, sulfuric acid, acetic acid, and ammonium chloride.
가수분해 반응 완결후 층분리하여 유기층을 소듐카보네이트 수용액과 물로 순차적으로 세척하고, 세척한 유기층을 마그네슘설페이트로 건조시킨 후 용매를 제거함으로써 고순도인 하기 화학식 2의 알파 알킬 퍼퓨랄 알콜을 수득할 수 있게된다.After completion of the hydrolysis reaction, the layers were separated and the organic layer was sequentially washed with aqueous sodium carbonate solution and water, the washed organic layer was dried over magnesium sulfate, and then the solvent was removed to obtain high purity alpha alkyl perfural alcohol of Formula 2 below. do.
[화학식 2][Formula 2]
여기서, R1 은 메틸, 에틸, R2는 수소, 메틸 또는 에틸그룹이다.Wherein R 1 is methyl, ethyl, R 2 is hydrogen, methyl or ethyl group.
이하, 본 발명을 실시예를 들어 더욱 상세히 설명하고자 하나, 본 발명이 하기 실시예에 의하여 제한되는 것은 아니다.Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited by the following Examples.
실시예1Example 1
4구 0.5ℓ 반응기에 메카니컬교반기, 온도계, 콘덴서, 가스버블링라인(gas bubbling line)을 설치하여, 반응기내부를 질소분위기로 만든 후 상온에서 마그네슘 24.3g(1mol), 테트라하이드로퓨란(함수율 300ppm) 82㎖, 톨루엔 66㎖를 차례로 주입하였다. 온도를 50℃로 승온시킨 후 디브로모에탄 0.86㎖(1mol%)를 넣었다. 이때 반응기 내부온도는 60℃까지 상승하였다. 그리고, 50∼60℃에서 10분간 교반하고, 20∼60℃를 유지하면서 가스버블링라인을 이용하여 가스상태인 에틸클로라이드 71g(1.1mol)을 약 3시간 동안 주입하여 그리너드 시약을 제조하였다. 반응이 진행됨에 따라 반응물은 짙은 회색의 슬러리(slurry) 상태가 되었다.A mechanical stirrer, thermometer, condenser, and gas bubbling line were installed in a four-necked 0.5ℓ reactor to make the inside of the reactor with a nitrogen atmosphere, and then magnesium at 24.3 g (1 mol) and tetrahydrofuran (water content 300 ppm) at room temperature. 82 ml and toluene 66 ml were injected one after the other. After the temperature was raised to 50 ° C., 0.86 ml (1 mol%) of dibromoethane was added thereto. At this time, the temperature inside the reactor was raised to 60 ℃. Then, the mixture was stirred at 50 to 60 ° C. for 10 minutes, and 71 g (1.1 mol) of ethyl chloride in a gaseous state was injected for about 3 hours using a gas bubbling line while maintaining 20 to 60 ° C. to prepare a Grignard reagent. As the reaction proceeded, the reactants became a dark gray slurry.
40∼55℃에서 상기 제조된 그리너드 시약에 퍼퓨랄 92.3g(0.96mol)을 1시간에 걸쳐 투입하고, 상온에서 30% 초산 수용액을 넣은 후 30분간 교반하고, 정제하여 유기층을 층분리 하였다. 층분리하여 얻어진 유기층을 15% 소듐카보네이트 수용액과 물로 세척하고, 세척한 유기층을 마그네슘 설페이트로 건조시킨 후 15∼30mmHg, 30∼50℃에서 테트라하이드로퓨란과 톨루엔을 제거하여 순도 97%인 엷은 갈색의 알파 에틸 퍼퓨릴 알콜 117g을 수득하였다. 수율은 퍼퓨랄을 기준으로 96%이었다.92.3 g (0.96 mol) of perfural was added to the prepared Grignard reagent at 40 to 55 ° C. over 1 hour, an aqueous 30% acetic acid solution was added thereto at room temperature, stirred for 30 minutes, and purified to separate an organic layer. The organic layer obtained by layer separation was washed with 15% aqueous sodium carbonate solution and water, and the washed organic layer was dried over magnesium sulfate, and then tetrahydrofuran and toluene were removed at 15 to 30 mmHg and 30 to 50 ° C. to obtain a light brown color of 97% purity. 117 g of alpha ethyl perfuryl alcohol were obtained. The yield was 96% based on perfural.
실시예 2Example 2
테트라하이드로퓨란 120㎖, 톨루엔 96㎖를 사용한 것을 제외하고는 실시예 1과 동일한 방법으로 실시하여 순도 99%인 엷은 갈색의 알파 에틸 퍼퓨릴 알콜 118g을 수득하였다. 수율은 퍼퓨랄 기준으로 97%이었다.118 g of light brown alpha ethyl perfuryl alcohol having a purity of 99% was obtained in the same manner as in Example 1, except that 120 ml of tetrahydrofuran and 96 ml of toluene were used. Yield was 97% on a perfural basis.
실시예 3Example 3
테트라하이드로퓨란 250㎖, 자일렌 250㎖를 사용한 것을 제외하고는 실시예 1과 동일한 방법으로 실시한 후 순도 99%인 엷은 갈색의 알파 에틸 퍼퓨릴 알콜 120g을 수득하였다. 수율은 퍼퓨랄 기준으로 99%이었다.120 g of light brown alpha ethyl perfuryl alcohol having a purity of 99% was obtained after the same procedure as in Example 1 except that 250 ml of tetrahydrofuran and 250 ml of xylene were used. The yield was 99% on a perfural basis.
실시예4Example 4
에틸클로라이드 68g(1.05mol)를 사용한 것을 제외하고는 실시예 1과 동일하게 실시하여 순도 96%인 엷은 갈색의 알파 에틸 퍼퓨릴 알콜 115g을 수득하였다. 수율은 퍼퓨랄 기준으로 95%이었다.Except for using 68g (1.05mol) of ethyl chloride was carried out in the same manner as in Example 1 to give 115g of light brown alpha ethyl perfuryl alcohol having a purity of 96%. The yield was 95% on a perfural basis.
실시예 5Example 5
메틸클로라이드 55g(1.2mol), 테트라하이드로퓨란 120㎖, 벤젠 96㎖를 사용한 것을 제외하고는 실시예 1과 동일한 방법으로 실시하여 순도 99%인 엷은 갈색의 알파 메틸 퍼퓨릴 알콜 106g을 수득하였다. 수율은 퍼퓨랄 기준으로 98%이었다.In the same manner as in Example 1, except that 55 g (1.2 mol) of methyl chloride, 120 mL of tetrahydrofuran and 96 mL of benzene were used, 106 g of light brown alpha methyl perfuryl alcohol having a purity of 99% was obtained. The yield was 98% on a perfural basis.
실시예 6Example 6
에틸브로마이드 114g(1.05mol)을 사용한 것을 제외하고는 실시예 1과 동일한 방법으로 실시하여 순도 99%인 엷은 갈색의 알파 에틸 퍼퓨릴 알콜 120g을 수득하였다. 수율은 퍼퓨랄 기준으로 99%이었다.120 g of light brown alpha ethyl perfuryl alcohol having a purity of 99% was obtained in the same manner as in Example 1, except that 114 g (1.05 mol) of ethyl bromide was used. The yield was 99% on a perfural basis.
실시예 7Example 7
디보로모에탄 대신 실시예 1에서 제조한 그리너드 시약 반응물을 2㎖ 사용한 것을 제외하고는 실시예 1과 동일한 방법으로 실시하여 순도 97%인 엷은 갈색의 알파 에틸 퍼퓨릴 알콜 117g을 수득하였다. 수율은 퍼퓨랄 기준으로 96%이었다.117 g of light brown alpha ethyl perfuryl alcohol having a purity of 97% was obtained in the same manner as in Example 1, except that 2 ml of the Greennard reagent reactant prepared in Example 1 was used instead of diboromoethane. The yield was 96% on a perfural basis.
비교예 Comparative example
반응용매로 무수에틸에테르를 사용하여 그리너드 시약을 제조한 후 여기에 퍼퓨랄을 첨가해 그리너드 반응을 완결시키고, 완결된 그리너드 반응물을 암모늄 클로라이드 수용액으로 가수분해 한 후 유기층을 분리하여 에틸에테르를 제거한 잔여물을 쇼트-칼럼(Shot column)장치에서 0.5mmHg로 감압증류하여 순도 90%의 알파메틸 퍼퓨릴 알콜을 수득하였다.To prepare a Grignard reagent using anhydrous ethyl ether as a reaction solvent, perfural was added thereto to complete the Grignard reaction. The Grignard reaction was hydrolyzed with an aqueous ammonium chloride solution, and the organic layer was separated. The residue from which was removed was distilled under reduced pressure at 0.5 mmHg in a shot column apparatus to obtain alphamethyl perfuryl alcohol having a purity of 90%.
이상에서 살펴본 바와 같이 알파 에틸 퍼퓨릴 알콜을 제조함에 있어서, 그리너드 시약 제조시 반응용매로서 테트라하이드로퓨란과 방향족 하이드로카본을 혼합한 것을 사용함으로써 퍼퓨랄을 첨가하여 수득되는 최종 생성물인 알파 알킬 퍼퓨릴 알콜의 순도 및 수율이 95% 이상의 고순도, 고수율을 나타내어 생산성 및 경제성에서 우수한 잇점을 갖는다.As described above, in preparing alpha ethyl perfuryl alcohol, alpha alkyl perfuryl, which is a final product obtained by adding perfural by using a mixture of tetrahydrofuran and aromatic hydrocarbon as a reaction solvent in the preparation of the greennard reagent The purity and yield of alcohol exhibits high purity, high yield of 95% or more, which has excellent advantages in productivity and economy.
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