KR20150064498A - A Method for Preparation of Ester Compound which Improve the Yield by Using an Acetone - Google Patents

A Method for Preparation of Ester Compound which Improve the Yield by Using an Acetone Download PDF

Info

Publication number
KR20150064498A
KR20150064498A KR1020130149299A KR20130149299A KR20150064498A KR 20150064498 A KR20150064498 A KR 20150064498A KR 1020130149299 A KR1020130149299 A KR 1020130149299A KR 20130149299 A KR20130149299 A KR 20130149299A KR 20150064498 A KR20150064498 A KR 20150064498A
Authority
KR
South Korea
Prior art keywords
ester compound
ester
yield
alcohol
acetone
Prior art date
Application number
KR1020130149299A
Other languages
Korean (ko)
Other versions
KR101709670B1 (en
Inventor
공명진
이원재
최용진
Original Assignee
주식회사 엘지화학
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to KR1020130149299A priority Critical patent/KR101709670B1/en
Publication of KR20150064498A publication Critical patent/KR20150064498A/en
Application granted granted Critical
Publication of KR101709670B1 publication Critical patent/KR101709670B1/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
    • C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
    • C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
    • C07D317/14—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D317/18—Radicals substituted by singly bound oxygen or sulfur atoms
    • C07D317/24—Radicals substituted by singly bound oxygen or sulfur atoms esterified
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/02—Apparatus characterised by being constructed of material selected for its chemically-resistant properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
    • B01J19/10—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing sonic or ultrasonic vibrations
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D319/00—Heterocyclic compounds containing six-membered rings having two oxygen atoms as the only ring hetero atoms
    • C07D319/04—1,3-Dioxanes; Hydrogenated 1,3-dioxanes

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

In the present invention, provided is a manufacturing method of novel ester compounds, which uses special synthesis conditions without additional solvents and catalysts and therefore significantly increases yield. The present invention relates to a manufacturing method of ester compounds where formic acid is injected into a mixture of alcohol and acetone and ultrasonic waves are assigned to the same, thereby inducing an ester reaction and ester compounds manufactured by the method.

Description

아세톤을 이용하여 수율을 개선한 에스터 화합물의 제조방법{A Method for Preparation of Ester Compound which Improve the Yield by Using an Acetone}BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a method for preparing an ester compound having improved yield using acetone,

본 발명은 에스터 화합물의 제조방법에 관한 것으로서, 보다 상세하게는 아세톤을 이용하여 수율을 개선한 에스터 화합물의 제조방법에 관한 것이다.The present invention relates to a process for producing an ester compound, and more particularly, to a process for producing an ester compound in which yield is improved by using acetone.

에스터(ester)는 알코올이 산과 반응하여 물을 잃고 축합 반응하여 생성된 화합물로서, 주로 카르복실산 에스터를 의미한다. An ester is a compound produced by an alcohol reacting with an acid to lose water and condensation reaction, and mainly means a carboxylic acid ester.

이러한 에스터 화합물의 제조방법으로서, 종래에는 Selective Esterifications of Primary Alcohols in a Water-Containing Solvent; Yong Wang, Bilal A. Aleiwi, Qinghui 0Wang and Michio Kurosu; Org. Lett., 2012, 14 (18), pp 4910-4913에서와 같이, 추가 용매 및 촉매의 존재 하에서 알코올과 산을 반응시켜 에스터화 반응을 통해 에스터 화합물을 합성하고 있다. As a method for producing such an ester compound, there has been known a process for producing a mixture of Selective Esters of Primary Alcohols in a Water-Containing Solvent; Yong Wang, Bilal A. Aleiwi, Qinghui 0Wang and Michio Kurosu; Org. Lett., 2012, 14 (18), pp 4910-4913, an ester compound is synthesized through an esterification reaction by reacting an alcohol with an acid in the presence of an additional solvent and a catalyst.

그러나, 종래의 방법에 의하면, 추가 용매 및 촉매의 사용에 따라 경제성이 떨어지는 등의 문제가 많이 발생하였다. 따라서, 일반적으로 사용되는 추가 용매 및 촉매의 사용 없이도 에스터화 반응의 수율을 크게 높일 수 있는, 새로운 에스터 화합물의 합성방법에 대한 연구가 필요한 실정이다.
However, according to the conventional method, many problems such as poor economical efficiency have arisen due to the use of an additional solvent and a catalyst. Therefore, there is a need for studies on the synthesis of new ester compounds, which can greatly increase the yield of the esterification reaction without the use of commonly used additional solvents and catalysts.

Selective Esterifications of Primary Alcohols in a Water-Containing Solvent; Yong Wang, Bilal A. Aleiwi, Qinghui Wang and Michio Kurosu; Org. Lett., 2012, 14 (18), pp 4910-4913Selective Esterifications of Primary Alcohols in a Water-Containing Solvent; Yong Wang, Bilal A. Aleiwi, Qinghui Wang and Michio Kurosu; Org. Lett., 2012, 14 (18), pp 4910-4913

상기와 같은 종래기술의 문제점을 해결하고자, In order to solve the above problems of the prior art,

본 발명은 추가 용매 및 촉매의 사용 없이도, 특수한 합성 조건을 사용하여 수율을 크게 높일 수 있는, 새로운 에스터 화합물의 제조방법을 제공하는 것을 목적으로 한다.
It is an object of the present invention to provide a process for producing a novel ester compound which can greatly increase the yield by using special synthesis conditions without the use of additional solvents and catalysts.

상기의 목적을 달성하기 위하여, In order to achieve the above object,

본 발명은 알코올 및 아세톤의 혼합물에 포름산을 투입한 후, 초음파를 인가하여 에스터 반응을 유도하는 에스터 화합물의 제조방법을 제공한다.
The present invention provides a method for producing an ester compound, which comprises introducing formic acid into a mixture of alcohol and acetone, and then applying ultrasonic waves to induce an ester reaction.

또한, 본 발명은 상기 제조방법에 의하여 제조된 에스터 화합물을 제공한다.
In addition, the present invention provides an ester compound produced by the above production method.

본 발명의 에스터 화합물의 제조방법에 따르면, According to the method for producing an ester compound of the present invention,

추가 용매 및 촉매의 사용 없이도, 특수한 합성 조건을 사용하여 수율을 크게 높일 수 있다는 장점이 있다.Without the use of additional solvents and catalysts, there is an advantage in that yield can be greatly increased by using special synthesis conditions.


이하 본 발명의 에스터 화합물의 제조방법 및 상기 제조방법에 의하여 제조된 에스터 화합물에 대하여 상세하게 설명한다.
Hereinafter, the method for producing the ester compound of the present invention and the ester compound produced by the above method will be described in detail.

본 발명은 기존과 같이 황산과 같은 강산 촉매 및 추가 용매를 사용하여 에스터 화합물을 제조하는 것이 아니라, 촉매 및 추가 용매를 사용하지 않고도 알코올과 아세톤에 포름산을 반응시켜 에스터 화합물을 제조하는 방법에 관한 것이다. 따라서, 에스터 화합물의 제조 공정이 기존에 비해 적은 비용이 들면서도, 에스터 화합물의 수율을 향상시킬 수 있다.
The present invention relates to a method for producing an ester compound by reacting formic acid with an alcohol and an acetone without using a catalyst and an additional solvent, instead of preparing an ester compound using a strong acid catalyst such as sulfuric acid and an additional solvent . Therefore, it is possible to improve the yield of the ester compound, even though the production process of the ester compound is less expensive than the conventional process.

이를 위하여, 본 발명의 에스터 화합물의 제조방법은 하기 반응식 1과 같이, 알코올 및 아세톤의 혼합물에 포름산을 투입한 후, 초음파를 인가하여 에스터 반응을 유도하여 에스터 화합물을 제조한다.To this end, the ester compound of the present invention is prepared by introducing formic acid into a mixture of alcohol and acetone, and then applying an ultrasonic wave to induce ester reaction to produce an ester compound.

[반응식 1][Reaction Scheme 1]

Figure pat00001
Figure pat00001

상기 반응식 1과 같이, 본 발명의 에스터 화합물의 제조방법에 의하여 (2,2-Dimethyl-1,3-dioxolan-4-yl) methanol과 2,2-Dimethyl-1,3-dioxan-5-ol을 포름산과 반응시키면, (2,2-Dimethyl-1,3-dioxolan-4-yl) methyl formate와 2,2-Dimethyl-1,3-dioxan-5-yl formate이 생성된다. 본 발명의 에스터 화합물의 제조방법은, 에스터 화합물의 선택도 및 최종 수율을 향상시키기 위하여, 다음과 같은 특징을 갖는다.
(2,2-Dimethyl-1,3-dioxolan-4-yl) methanol and 2,2-dimethyl-1,3-dioxan-5-ol (2,2-Dimethyl-1,3-dioxolan-4-yl) methyl formate and 2,2-Dimethyl-1,3-dioxan-5-yl formate are produced by reaction with formic acid. The method for producing an ester compound of the present invention has the following characteristics in order to improve selectivity and final yield of an ester compound.

본 발명의 에스터 화합물의 제조방법에 있어서, 상기 알코올은 에스터화 반응에 사용되는 것이라면 특별한 제한은 없으나, 바람직하게는 2,2-Dimethyl-1,3-dioxolan-4-yl) methanol, 2,2-Dimethyl-1,3-dioxan-5-ol 또는 glycerol을 사용할 수 있다.
In the process for producing the ester compound of the present invention, the alcohol is not particularly limited as long as it is used in the esterification reaction. Preferably, 2,2-dimethyl-1,3-dioxolan- -Dimethyl-1,3-dioxan-5-ol or glycerol.

본 발명의 에스터 화합물의 제조방법에 있어서, 아세톤은 에스터 반응에 사용하는 것이라면 통상의 구입 가능한 것을 특별한 제한 없이 사용할 수 있으며, 바람직하게는 순도 40 내지 99.5%의 아세톤을 사용할 수 있다. 본 발명에 있어서, 상기 아세톤은 알코올을 기준으로 3 내지 15 당량비로 투입하여 사용할 수 있다. 상기 아세톤이 3 당량비 미만으로 사용되면 알코올의 전환률 및 에스터 반응의 선택도가 떨어질 수 있고, 15 당량비를 초과하여 사용하더라고, 추가에 따른 특별한 효과의 상승이 없다.
In the process for producing an ester compound of the present invention, acetone is not particularly limited as long as it can be used in the ester reaction, and acetone having a purity of 40 to 99.5% can be used. In the present invention, the acetone may be used in an amount of 3 to 15 equivalents based on the alcohol. If the acetone is used in an amount less than 3 equivalents, the conversion of alcohol and the selectivity of ester reaction may be lowered, and even if the acetone is used in excess of 15 equivalent ratios, there is no increase in specific effect due to addition.

본 발명의 에스터 화합물의 제조방법에 있어서, 포름산은 알코올을 기준으로 1 내지 5 당량비로 투입된다. 상기 포름산이 1 당량비 미만으로 사용되면 알코올의 전환률 및 에스터 화합물의 선택도가 떨어질 수 있고, 5 당량비를 초과하여 사용하더라고, 추가에 따른 특별한 효과의 상승이 없다.
In the method for producing the ester compound of the present invention, formic acid is added in an amount of 1 to 5 equivalents based on the alcohol. If the formic acid is used in an amount less than 1 equivalent, the conversion of the alcohol and the selectivity of the ester compound may be lowered, and even if the amount is more than 5 equivalents, there is no increase in the specific effect.

본 발명의 에스터 화합물의 제조방법에 있어서, 초음파의 세기는 사용자의 필요에 따라서 적절하게 조절될 수 있으나 바람직하게는 20W/cm2 ~ 700W/cm2의 파워 밀도(power density)로 인가될 수 있으며, 더욱 바람직하게는 70W/cm2 ~ 500W/cm2의 파워 밀도(power density)로 될 수 있다. 초음파 파워 밀도가 20 W/cm2 미만으로 너무 낮으면, 미반응으로 인한 반응 효율의 저하 등의 문제점이 있으며, 초음파 파워 밀도가 700 W/cm2 초과로 너무 높으면 반응 용액이 과열되는 문제점이 있으므로 바람직하지 않다. 또한, 상기 초음파 반응의 시간은 사용자의 필요에 따라서 적절하게 조절될 수 있으나 바람직하게는 10 분 내지 400 분 동안 인가될 수 있으며, 더욱 바람직하게는 30 분 내지 100 분 동안 인가될 수 있다.
In the production method according to the present invention, ester compounds, the ultrasonic intensity can be properly adjusted according to the user's needs, but preferably at a power density of 20W / cm 2 ~ 700W / cm 2 can be applied to the (power density), and , More preferably from 70 W / cm 2 to 500 W / cm 2 . Ultrasonic if the power density is too low, less than 20 W / cm 2, there is a problem such as a reduction in reaction efficiency due to unreacted, it is a problem that the ultrasonic power density is too high, the reaction mixture is overheated to 700 W / cm 2 than It is not preferable. In addition, the time of the ultrasonic reaction can be suitably adjusted according to the user's needs, but it can be applied for 10 minutes to 400 minutes, and more preferably for 30 minutes to 100 minutes.

본 발명의 에스터 화합물의 제조방법에 있어서, 상기 알코올과 아세톤에 포름산을 첨가한 후의 에스터 반응은 -20 내지 10℃의 반응온도에서 수행할 수 있다. 상기 반응온도가 -20℃ 내지 10℃의 범위일 때 최적의 반응성을 갖게 되며, 상기 범위 밖에서는 반응성이 급속하게 떨어지는 문제가 있다.
In the method for producing an ester compound of the present invention, the ester reaction after adding formic acid to the alcohol and acetone may be carried out at a reaction temperature of -20 to 10 ° C. When the reaction temperature is in the range of -20 占 폚 to 10 占 폚, it has the optimum reactivity, and outside the above range, the reactivity is rapidly deteriorated.

본 발명은 상기의 제조방법에 의하여 제조된 에스터 화합물을 제공한다.The present invention provides an ester compound produced by the above-mentioned production method.

상기의 제조방법에 의하여 제조된 본 발명의 에스터 화합물은 수율이 40% 이상, 바람직하게는 수율이 50% 이상이기 때문에, 경제성이 뛰어나다.
The ester compound of the present invention produced by the above production method is excellent in economy because the yield is 40% or more, preferably 50% or more.

상기의 제조방법에 의하여 제조된 본 발명의 에스터 화합물은 2,2-Dimethyl-1,3-dioxolan-4-yl) methyl formate, 2,2-Dimethyl-1,3-dioxan-5-yl formate, glyceryl formate 또는 2-hydroxypropane-1,3-diyl diformate 등일 수 있다.
The ester compound of the present invention produced by the above process is a 2,2-dimethyl-1,3-dioxolan-4-yl methyl formate, 2,2-dimethyl- glyceryl formate or 2-hydroxypropane-1,3-diyl diformate.

이하 본 발명의 이해를 돕기 위하여 바람직한 실시예를 제시하나, 하기 실시예는 본 발명을 예시하는 것일 뿐 본 발명의 범주 및 기술사상 범위 내에서 다양한 변경 및 수정이 가능함은 당업자에게 있어서 명백한 것이며, 이러한 변경 및 수정이 첨부된 특허청구범위에 속하는 것도 당연한 것이다.
It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the scope and spirit of the invention as disclosed in the accompanying claims. Changes and modifications may fall within the scope of the appended claims.

실시예Example

에스터 화합물의 제조 Preparation of ester compounds

[실시예 1] [Example 1]

0.07 mol의 알코올(2,2-Dimethyl-1,3-dioxolan-4-yl)methanol 및 2,2-Dimethyl-1,3-dioxan-5-ol을 99:1로 혼합)과 잔량의 아세톤(5 eq)을 전 반응의 용매로 포함하는 알코올 용액 27.00g, 포름산 3.25g (0.07 mol, 1eq)을 플라스크 반응기에 투입한 후, circulator(줄라보 F32)를 0℃의 반응온도로 설정한 후, 초음파 반응기(Hielscher Ultrasonic GmbH. Model: UP400S)를 이용하여 85 W/cm2의 파워 밀도로 30 분간 초음파 처리하여 반응시켜 에스터 화합물을 제조하였다. 상기 초음파 반응기의 Maximum amplitude는 100㎛이었다.0.07 mol of 2,2-dimethyl-1,3-dioxolan-4-yl) methanol and 2,2-dimethyl-1,3-dioxan-5-ol in a ratio of 99: 1) (0.07 mol, 1 eq) of formic acid was placed in a flask reactor, and a circulator (Julalobo F32) was set to a reaction temperature of 0 ° C. Then, The ester compound was prepared by ultrasonication using a ultrasonic reactor (Hielscher Ultrasonic GmbH Model: UP400S) at a power density of 85 W / cm2 for 30 minutes. The maximum amplitude of the ultrasonic reactor was 100 탆.

[실시예 2][Example 2]

포름산을 4.875g (0.105 mol, 1.5 eq) 사용한 것을 제외하고는 실시예 1과 동일한 방법으로 에스터 화합물을 제조하였다.The ester compound was prepared in the same manner as in Example 1, except that 4.875 g (0.105 mol, 1.5 eq) of formic acid was used.

[실시예 3][Example 3]

포름산을 6.5g (0.14 mol, 2 eq) 사용한 것을 제외하고는 실시예 1과 동일한 방법으로 에스터 화합물을 제조하였다.The ester compound was prepared in the same manner as in Example 1, except that 6.5 g (0.14 mol, 2 eq) of formic acid was used.

[실시예 4][Example 4]

포름산을 9.75g (0.21 mol, 3 eq) 사용한 것을 제외하고는 실시예 1과 동일한 방법으로 에스터 화합물을 제조하였다.The ester compound was prepared in the same manner as in Example 1, except that 9.75 g (0.21 mol, 3 eq) of formic acid was used.

[실시예 5][Example 5]

포름산을 13g (0.28 mol, 4 eq) 사용한 것을 제외하고는 실시예 1과 동일한 방법으로 에스터 화합물을 제조하였다.The ester compound was prepared in the same manner as in Example 1 except that 13 g (0.28 mol, 4 eq) of formic acid was used.

[실시예 6][Example 6]

초음파 처리 시간을 1시간으로 한 것을 제외하고는 실시예 5와 동일한 방법으로 에스터 화합물을 제조하였다.An ester compound was prepared in the same manner as in Example 5 except that the ultrasonic treatment time was changed to 1 hour.

[실시예 7][Example 7]

초음파 처리 시간을 1.5시간으로 한 것을 제외하고는 실시예 5와 동일한 방법으로 에스터 화합물을 제조하였다.The ester compound was prepared in the same manner as in Example 5 except that the ultrasonic treatment time was changed to 1.5 hours.

[실시예 8][Example 8]

반응온도를 -10℃로 설정하고, 상기 초음파 반응기의 Maximum amplitude를 210㎛로 설정한 것을 제외하고는 실시예 5와 동일한 방법으로 에스터 화합물을 제조하였다.An ester compound was prepared in the same manner as in Example 5 except that the reaction temperature was set at -10 ° C and the maximum amplitude of the ultrasonic reactor was set at 210 μm.

[실시예 9][Example 9]

반응온도를 0℃로 설정한 것을 제외하고는 실시예 8과 동일한 방법으로 에스터 화합물을 제조하였다.An ester compound was prepared in the same manner as in Example 8 except that the reaction temperature was set at 0 占 폚.

[실시예 10][Example 10]

반응온도를 25℃로 설정한 것을 제외하고는 실시예 8과 동일한 방법으로 에스터 화합물을 제조하였다.The ester compound was prepared in the same manner as in Example 8 except that the reaction temperature was set at 25 캜.

[실시예 11][Example 11]

반응온도를 50℃로 설정한 것을 제외하고는 실시예 8과 동일한 방법으로 에스터 화합물을 제조하였다.An ester compound was prepared in the same manner as in Example 8 except that the reaction temperature was set to 50 캜.

[비교예 1] [Comparative Example 1]

포름산을 13g (0.28 mol, 4 eq) 사용하고, 초음파 반응 대신, 70℃에서 reflux로 1시간 동안 반응시킨 것을 제외하고는 실시예 1과 동일한 방법으로 에스터 화합물을 제조하였다.
The ester compound was prepared in the same manner as in Example 1, except that 13 g (0.28 mol, 4 eq) of formic acid was used and that the reaction was carried out at 70 캜 for 1 hour instead of ultrasonic reaction.

상기 실시예 1 내지 실시예 11 및 비교예 1의 반응 조건을 하기 표 1에 나타내었다.The reaction conditions of Examples 1 to 11 and Comparative Example 1 are shown in Table 1 below.

포름산(eq)Formic acid (eq) 반응온도(℃)Reaction temperature (캜) sonotrode
Maximum amplitude (㎛)sonotrode
Maximum amplitude (㎛) 반응시간 (H)Reaction time (H) 실시예 1Example 1 1.01.0 00 100100 0.50.5 실시예 2Example 2 1.51.5 00 100100 0.50.5 실시예 3Example 3 2.02.0 00 100100 0.50.5 실시예 4Example 4 3.03.0 00 100100 0.50.5 실시예 5Example 5 4.04.0 00 100100 0.50.5 실시예 6Example 6 4.04.0 00 100100 1.01.0 실시예 7Example 7 4.04.0 00 100100 1.51.5 실시예 8Example 8 4.04.0 -10-10 210210 0.50.5 실시예 9Example 9 4.04.0 00 210210 0.50.5 실시예 10Example 10 4.04.0 2525 210210 0.50.5 실시예 11Example 11 4.04.0 5050 210210 0.50.5 비교예 1Comparative Example 1 3.03.0 7070 -- 1.01.0

실험예Experimental Example

상기 실시예 및 비교예에서 제조한 에스터 화합물에 대하여, 가스 크로마토그래피(GC 6890N, agilent)를 이용하여, 미반응 알코올, 에스터 화합물을 GC area % 분석을 통하여 분석하였다. 알코올 전환율 및 에스터화 반응 선택도, 에스터화 반응 수율을 하기 식 1 내지 3을 이용하여 계산하였으며, 그 결과를 표 2에 나타내었다.The ester compounds prepared in the above Examples and Comparative Examples were analyzed by GC area% analysis using gas chromatography (GC 6890N, agilent), unreacted alcohol and ester compounds. Alcohol conversion and esterification selectivity, and esterification reaction yield were calculated using the following formulas 1 to 3, and the results are shown in Table 2.

[식 1][Formula 1]

알코올 전환율 (conversion, %) = 100- 반응 후 알코올 GC area%Alcohol conversion (conversion,%) = 100- Alcohol after reaction GC area%

[식 2][Formula 2]

에스터화 반응 선택도 (selectivity, %) = 100ⅹ(생성된 에스터 화합물 GC area%)/(알코올 전환율)Esterification selectivity (%) = 100 × (Ester compound GC area%) / (Alcohol conversion rate)

[식 3][Formula 3]

에스터화 반응 수율 (yield, %) = (알코올 전환율 ⅹ 에스터화 반응 선택도)/(100)Esterification yield (yield,%) = (alcohol conversion rate x esterification selectivity) / (100)

알코올 전환율 (conversion, %Alcohol conversion (conversion,%) 에스터화 반응 선택도 (selectivity, %)Esterification selectivity (%) 에스터화 반응 수율 (yield, %)Esterification yield (yield,%) 실시예 1Example 1 32.332.3 79.679.6 25.725.7 실시예 2Example 2 41.241.2 82.882.8 34.134.1 실시예 3Example 3 55.855.8 75.275.2 4242 실시예 4Example 4 46.846.8 89.389.3 41.841.8 실시예 5Example 5 50.550.5 90.990.9 45.945.9 실시예 6Example 6 73.273.2 62.462.4 45.745.7 실시예 7Example 7 80.780.7 76.276.2 61.561.5 실시예 8Example 8 42.442.4 94.394.3 40.040.0 실시예 9Example 9 61.961.9 89.289.2 55.255.2 실시예 10Example 10 54.754.7 71.371.3 39.039.0 실시예 11Example 11 73.173.1 60.060.0 43.743.7 비교예 1Comparative Example 1 75.275.2 40.040.0 30.130.1

상기 표 2에서 나타낸 바와 같이, 본 발명의 에스터 화합물의 제조방법에 의하여 제조한 실시예 1 내지 실시예 11의 경우, 모두 40% 이상의 수율을 가지며, 특히 실시예 7 및 실시예 9의 경우 50% 이상의 수율을 갖는 것으로 나타나, 비교예 1의 경우에 비하여 수율이 높게 나타나는 것을 알 수 있었다. 따라서, 본 발명의 실시예 1 내지 11의 제조 방법으로 에스터 화합물을 제조하는 경우, 추가의 용매 및 촉매를 사용하지 않고도 우수한 수율을 나타낸다는 것을 확인할 수 있었다.
As shown in Table 2, all of Examples 1 to 11 prepared by the method for producing an ester compound of the present invention had a yield of 40% or more, especially 50% or more in the case of Examples 7 and 9, And the yield was higher than that of Comparative Example 1. As a result, Thus, it was confirmed that when the ester compounds of Examples 1 to 11 of the present invention were prepared, excellent yield was obtained without using any additional solvent and catalyst.

Claims (14)

알코올 및 아세톤의 혼합물에 포름산을 투입한 후, 초음파를 인가하여 에스터 반응을 유도하는 에스터 화합물의 제조방법.A method for producing an ester compound, wherein formic acid is added to a mixture of alcohol and acetone, and then an ultrasonic wave is applied to induce an ester reaction. 청구항 1에 있어서,
상기 알코올은 2,2-Dimethyl-1,3-dioxolan-4-yl) methanol 또는 2,2-Dimethyl-1,3-dioxan-5-ol인 것을 특징으로 하는 에스터 화합물의 제조방법.The method according to claim 1,
Wherein the alcohol is 2,2-dimethyl-1,3-dioxolan-4-yl) methanol or 2,2-dimethyl-1,3-dioxan-5-ol. 청구항 1에 있어서,
상기 초음파는 20 W/cm2 ~ 700 W/cm2의 파워 밀도(power density)로 인가하는 것을 특징으로 하는 에스터 화합물의 제조방법.The method according to claim 1,
Wherein the ultrasonic wave is applied at a power density of 20 W / cm 2 to 700 W / cm 2 . 청구항 1에 있어서,
상기 초음파는 70 W/cm2 ~ 500 W/cm2의 파워 밀도(power density)로 인가하는 것을 특징으로 하는 에스터 화합물의 제조방법.The method according to claim 1,
Wherein the ultrasonic wave is applied at a power density of 70 W / cm 2 to 500 W / cm 2 . 청구항 1에 있어서,
상기 초음파는 10 분 ~ 400분 동안 인가하는 것을 특징으로 하는 에스터 화합물의 제조방법.The method according to claim 1,
Wherein the ultrasonic wave is applied for 10 minutes to 400 minutes. 청구항 1에 있어서,
상기 초음파는 30 분 ~ 100분 동안 인가하는 것을 특징으로 하는 에스터 화합물의 제조방법.The method according to claim 1,
Wherein the ultrasonic wave is applied for 30 minutes to 100 minutes. 청구항 1에 있어서,
상기 아세톤은 알코올을 기준으로 3 내지 15 당량비로 투입하는 것을 특징으로 하는 에스터 화합물의 제조방법.The method according to claim 1,
Wherein the acetone is added in an amount of 3 to 15 equivalents based on the alcohol. 청구항 1에 있어서,
상기 포름산은 알코올을 기준으로 1 내지 5 당량비로 투입하는 것을 특징으로 하는 에스터 화합물의 제조방법.The method according to claim 1,
Wherein the formic acid is added in an amount of 1 to 5 equivalents based on the alcohol. 청구항 1에 있어서,
상기 에스터 반응은 -20 내지 10℃의 온도에서 수행되는 것을 특징으로 하는 에스터 화합물의 제조방법.The method according to claim 1,
Wherein the ester reaction is carried out at a temperature of from -20 to < RTI ID = 0.0 > 10 C. < / RTI > 청구항 1에 있어서,
상기 에스터의 수율이 40% 이상인 것을 특징으로 하는 에스터 화합물의 제조방법.The method according to claim 1,
Wherein the yield of the ester is 40% or more. 청구항 1에 있어서,
상기 에스터의 수율이 50% 이상인 것을 특징으로 하는 에스터 화합물의 제조방법.The method according to claim 1,
Wherein the yield of the ester is 50% or more. 청구항 1에 있어서,
상기 에스터 화합물은 2,2-Dimethyl-1,3-dioxolan-4-yl) methyl formate 또는 2,2-Dimethyl-1,3-dioxan-5-yl formate인 것을 특징으로 하는 에스터 화합물의 제조방법.The method according to claim 1,
Wherein the ester compound is 2,2-dimethyl-1,3-dioxolan-4-yl methyl formate or 2,2-dimethyl-1,3-dioxan-5-yl formate. 청구항 1의 제조방법에 의하여 제조된 것을 특징으로 하는 에스터 화합물.The ester compound according to claim 1, which is produced by the process of claim 1. 청구항 13에 있어서,
상기 에스터 화합물은 2,2-Dimethyl-1,3-dioxolan-4-yl) methyl formate 또는 2,2-Dimethyl-1,3-dioxan-5-yl formate인 것을 특징으로 하는 에스터 화합물.
14. The method of claim 13,
Wherein the ester compound is 2,2-Dimethyl-1,3-dioxolan-4-yl) methyl formate or 2,2-Dimethyl-1,3-dioxan-5-yl formate.
KR1020130149299A 2013-12-03 2013-12-03 A Method for Preparation of Ester Compound which Improve the Yield by Using an Acetone KR101709670B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
KR1020130149299A KR101709670B1 (en) 2013-12-03 2013-12-03 A Method for Preparation of Ester Compound which Improve the Yield by Using an Acetone

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
KR1020130149299A KR101709670B1 (en) 2013-12-03 2013-12-03 A Method for Preparation of Ester Compound which Improve the Yield by Using an Acetone

Publications (2)

Publication Number Publication Date
KR20150064498A true KR20150064498A (en) 2015-06-11
KR101709670B1 KR101709670B1 (en) 2017-02-23

Family

ID=53503044

Family Applications (1)

Application Number Title Priority Date Filing Date
KR1020130149299A KR101709670B1 (en) 2013-12-03 2013-12-03 A Method for Preparation of Ester Compound which Improve the Yield by Using an Acetone

Country Status (1)

Country Link
KR (1) KR101709670B1 (en)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06111366A (en) * 1992-09-24 1994-04-22 Ricoh Co Ltd Optical information recording medium and its production
WO2008084227A1 (en) * 2007-01-12 2008-07-17 Halliburton Energy Services, Inc. Surfactant wash treatment fluids and associated methods
JP2009138098A (en) * 2007-12-06 2009-06-25 Saitama Univ Esterification method of free fatty acid and method for producing fatty acid ester fuel using it

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06111366A (en) * 1992-09-24 1994-04-22 Ricoh Co Ltd Optical information recording medium and its production
WO2008084227A1 (en) * 2007-01-12 2008-07-17 Halliburton Energy Services, Inc. Surfactant wash treatment fluids and associated methods
JP2009138098A (en) * 2007-12-06 2009-06-25 Saitama Univ Esterification method of free fatty acid and method for producing fatty acid ester fuel using it

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
ORG LETT. 2012 SEP 21; 14(18): 4910-4913 *
Selective Esterifications of Primary Alcohols in a Water-Containing Solvent; Yong Wang, Bilal A. Aleiwi, Qinghui Wang and Michio Kurosu; Org. Lett., 2012, 14 (18), pp 4910-4913

Also Published As

Publication number Publication date
KR101709670B1 (en) 2017-02-23

Similar Documents

Publication Publication Date Title
RU2014138169A (en) CATALYST AND METHOD FOR PRODUCING ACETIC ACID AND DIMETHYL ETHER
TW200710076A (en) Process for producing aldehyde with 2-position branched long-chain alkyl
RU2016145670A (en) IMPROVED CATALYTIC CHARACTERISTICS IN METHODS FOR PRODUCING ACETIC ACID
KR101679717B1 (en) A Method for Preparation of Allyl alcohol and the Allyl alcohol Prepared by the Same
KR101709670B1 (en) A Method for Preparation of Ester Compound which Improve the Yield by Using an Acetone
Ren et al. A simple procedure for the esterification and transesterification using p-toluene sulfonic acid as catalyst
JP2015510932A5 (en)
KR101634220B1 (en) A Method for Preparation of Ester Compound and the Ester Compound manufactured by the Same
KR102492874B1 (en) Method for producing cyclobutane tetracarboxylic acid derivative
KR102162857B1 (en) Method for processing by-products of 1,4-cyclohexanedimethanol
KR20160001054A (en) Method for preparing ester compound using sulfonic acid or sulfonate catalysts
JP5969581B2 (en) Method for producing ester compound and ester compound produced thereby
KR101602428B1 (en) Method for preparing glycidol through successive catalytic reaction
KR101703159B1 (en) A Method for Preparation of Solketal
CN110878025A (en) Method for reducing aromatic nitro compound into aromatic amine compound
KR20160141953A (en) An efficient process of preparation of 2-(Undecyloxy)-ethanol for production in large scale
KR101293818B1 (en) METHOD FOR PREPARING α, β-UNSATURATED ALDEHYDE
He et al. Oleylamine-catalyzed tandem Knoevenagel/Michael addition of 1, 3-cyclohexanediones with aromatic aldehydes
KR102055927B1 (en) Process for preparing acrolein
CN112920028B (en) Method for preparing aldehyde compound by olefin oxidation
TW202000636A (en) Process for preparing bis(2-hydroxyethyl) terephthalate
CN104341294B (en) A kind of method being prepared 4-methoxyl group methyl valerate by γ-valerolactone
KR101559532B1 (en) Method for preparing levulinic acid using solid acid catalyst under biomass-derived ethylene glycol-based solvent
KR20150131515A (en) A Method for Preparation of Allyl Formate
JP2009046415A (en) Method for producing ester

Legal Events

Date Code Title Description
A201 Request for examination
E902 Notification of reason for refusal
E701 Decision to grant or registration of patent right
GRNT Written decision to grant