KR19980014628A - Preparation of 2- (4-dibutylamino-2-hydroxybenzoyl) benzoic acid - Google Patents
Preparation of 2- (4-dibutylamino-2-hydroxybenzoyl) benzoic acid Download PDFInfo
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Abstract
본 발명은 다음 구조식(Ⅰ)로 표시되는 2-(4-디부틸아미노-2-히드록시벤조일)벤조산의 제조방법에 관한 것으로서, 더욱 상세하게 설명하면 m-아미노페놀을 출발물질로 하여 다음 구조식(Ⅰ)로 표시되는 2-(4-디부틸아미노-2-히드록시벤조일)벤조산을 제조하는 통상의 제조방법에 있어서, m-아미노페놀과 부틸 할라이드를 반응시킬때 산화마그네슘 또는 트리에틸아민을 염기로 사용하고 유기용매 대신에 물을 용매로 사용하거나 또는 반응용매 없이 반응을 수행하여 경제적으로 유리한 효과를 가지고, 또한 반응이 완전히 완료된 후에 수산화나트륨용액을 사용한 염석(salting out) 효과에 의해 목적 화합물을 분리·정제하므로 통상적으로 불순물로서 존재하는 로다민계 화합물의 존재를 완전히 배제할 수 있는 효과를 가지는 새로운 2-(4-디부틸아미노-2-히드록시벤조일)벤조산의 제조방법에 관한 것이다.The present invention relates to a process for preparing 2- (4-dibutylamino-2-hydroxybenzoyl) benzoic acid represented by the following structural formula (I), more specifically, (4-dibutylamino-2-hydroxybenzoyl) benzoic acid represented by the following formula (I), in the case of reacting m-aminophenol with a butyl halide, magnesium oxide or triethylamine The objective compound is obtained by salting out using a sodium hydroxide solution after the reaction is completely completed, using an organic solvent instead of water as a solvent, or performing a reaction without using a reaction solvent, (4-dibutylamino-2-hydroxyne-2-ene), which has the effect of completely eliminating the presence of a rhodamine compound normally present as an impurity, Benzoyl) benzoic acid.
Description
본 발명은 2-(4-디부틸아미노-2-히드록시벤조일)벤조산의 제조방법에 관한 것으로서, 더욱 상세하게 설명하면 m-아미노페놀을 출발물질로 하여 감열지에 사용되는 염료의 중간체로 널리 이용되고 있는 다음 구조식(Ⅰ)로 표시되는 2-(4-디부틸아미노-2-히드록시벤조일)벤조산을 제조하는 통상의 제조방법에 있어서, m-아미노페놀과 부틸 할라이드를 반응시킬때 산화마그네슘 또는 트리에틸아민을 염기로 사용하고 유기용매 대신에 물을 용매로 사용하거나 또는 반응용매 없이 반응을 수행하여 경제적으로 유리한 효과를 가지고, 또한 반응이 완전히 완료된 후에 수산화나트륨용액을 사용한 염석효과에 의해 목적 화합물을 분리·정제하므로 통상적으로 불순물로서 존재하는 로다민계 화합물의 존재를 완전히 배제할 수 있는 효과를 가지는 새로운 2-(4-디부틸아미노-2-히드록시벤조일)벤조산의 제조방법에 관한 것이다.More particularly, the present invention relates to a process for preparing 2- (4-dibutylamino-2-hydroxybenzoyl) benzoic acid, which is widely used as an intermediate of dyes used in thermal paper using m- (4-dibutylamino-2-hydroxybenzoyl) benzoic acid, which is represented by the following structural formula (I), is reacted with m-aminophenol and butyl halide, magnesium oxide or It is economically advantageous to use triethylamine as a base and water as a solvent instead of an organic solvent or to carry out the reaction in the absence of a reaction solvent and to obtain a compound of interest by salting out with sodium hydroxide solution (4-dibutyl-4-iodobenzyl), which has an effect of completely eliminating the presence of a rhodamine compound usually present as an impurity, 2-hydroxybenzoyl) benzoic acid. ≪ / RTI >
상기 구조식(Ⅰ)로 표시되는 2-(4-디부틸아미노-2-히드록시벤조일)벤조산(이하, BBA라함)은 감열지 등에 사용되고 있는 플루오란 계통의 염료물질인 2-아닐리노-3-메틸-6-디부틸아미노플루오란 염료(ODBⅡ) 등의 중간체로 널리 이용되고 있다.2- (4-dibutylamino-2-hydroxybenzoyl) benzoic acid (hereinafter referred to as BBA) represented by the above structural formula (I) is a fluorane-based dye material used in thermal paper, -6-dibutylaminofluorane dyes (ODB II) and the like.
BBA로부터 ODBⅡ의 일반적인 합성과정은 다음 반응식 1로 표시될 수 있다.The general synthesis procedure of ODB II from BBA can be represented by the following reaction formula 1.
[반응식 1][Reaction Scheme 1]
본 발명에서 목적으로 하고 있는 상기 구조식(Ⅰ)로 표시되는 BBA의 제조방법에 대해서는 이미 여러 문헌에 제시되어 있는 바, 일반적으로 아미노페놀 유도체를 출발물질로 사용하여 이를 N-부틸화시켜 디부틸아미노페놀을 합성한 다음, 이를 다시 프탈산과 반응시켜 목적화합물을 얻고 있다. 특히 m-아미노페놀을 출발물질로 사용할 경우 반응성이 좋은 부틸 할라이드를 사용하거나 또는 반응온도나 압력을 높여서 반응성을 높이는데, 이러한 제조방법에서는 N-모노알킬 화합물은 쉽게 생성되나 N-모노알킬 화합물로부터 N-디알킬 화합물로의 변화는 쉽게 이루어지지 않으며, 또한 반응조건을 격렬하게 해주면 부산물이 생성되는 문제가 있었다. 따라서, m-아미노페놀을 출발물질로 하여 상기 구조식(Ⅰ)로 표시되는 BBA를 합성하는 과정에서 가장 까다로운 공정은 디부틸아미노 페놀의 합성공정이라 할 수 있다.The preparation method of BBA represented by the above structural formula (I) for the purpose of the present invention has already been described in various documents. Generally, the aminophenol derivative is used as a starting material and is N-butylated to obtain dibutylamino Phenol, which is then reacted with phthalic acid to obtain the desired compound. In particular, when m-aminophenol is used as a starting material, a highly reactive butyl halide is used, or the reaction temperature or pressure is increased to increase the reactivity. In this preparation method, the N-monoalkyl compound is easily produced, N-dialkyl compounds can not be easily changed, and if the reaction conditions are intensified, by-products are generated. Therefore, the most difficult process in the process of synthesizing BBA represented by the above structural formula (I) using m-aminophenol as a starting material is a process for synthesizing dibutylaminophenol.
아미노페놀로부터 디알킬아미노페놀을 합성하는 공정으로서 대표적인 방법이 다음과 같은 특허에 개시되어 있다.Representative processes for synthesizing dialkylaminophenols from aminophenols are disclosed in the following patents.
예컨대 일본특허공개 소62-258,346호에서는 다음 반응식 2에 나타낸 바와 같이 아미노페놀을 출발물질로 하고, 이를 수소기체 및 팔라듐(Pd) 또는 플라티늄(Pt) 촉매하에서 알킬알데히드를 반응시켜 디알킬아미노페놀을 제조하고 있다.For example, in JP-A-62-258,346, as shown in the following reaction formula 2, an aminophenol as a starting material is reacted with an alkylaldehyde under hydrogen gas and palladium (Pd) or platinum (Pt) .
[반응식 2][Reaction Scheme 2]
상기 제조방법에서는 수소를 사용하고 또한 촉매를 이용하여 고압 조건하에서 반응이 진행하므로 이를 위해서는 수소화반응장치 및 고압반응장치 등 부가적인 장치설비가 필요하고 공정이 매우 까다로운 문제가 있다.In the above production process, since the reaction proceeds under high pressure using hydrogen and a catalyst, additional equipment such as a hydrogenation apparatus and a high-pressure reaction apparatus are required and the process is very troublesome.
또한, 일본특허공개 소62-48,653호에서는 다음 반응식 3에 나타낸 바와 같이 모노알킬화된 아미노페놀을 출발물질로 하고, 이를 암모니아 존재하에서 알킬 할라이드와 반응시켜 디알킬아미노페놀을 제조하고 있다.Japanese Patent Application Laid-Open No. 62-48,653 discloses a dialkylaminophenol as a starting material, which is monoalkylated as shown in the following reaction scheme 3, and reacting it with an alkyl halide in the presence of ammonia.
[반응식 3][Reaction Scheme 3]
상기 제조방법에서는 물을 용매로 하고 암모니아를 사용하는 장점이 있지만, 상압이 아닌 고압하에서 반응을 수행하여야 하므로 이 또한 고압반응장치가 필요하고 다단계의 제조공정을 거쳐야 하는 문제가 있다.In the above production method, although water is used as a solvent and ammonia is used, since the reaction must be performed under high pressure rather than atmospheric pressure, there is also a problem that a high-pressure reaction apparatus is required and a multi-stage production process is required.
또한, 일본특허공개 소62-61,995호에서는 다음 반응식 4에 나타낸 바와 같이 m-아미노페놀을 출발물질로 하고, 이를 수산화마그네슘(Mg(OH)2) 염기존재하에서 에틸 클로라이드와 반응시켜 m-디에틸아미노페놀을 제조하고 있다.In JP-A 62-61,995, as shown in the following reaction formula (4), m-amino phenol is used as a starting material and reacted with ethyl chloride in the presence of magnesium hydroxide (Mg (OH) 2 ) Aminophenol is produced.
[반응식 4][Reaction Scheme 4]
상기 제조공정은 고압하에서 수행되므로 작업상의 어려움이 있어 이를 공업적인 대량생산에 적용하는데는 한계가 있다.Since the above manufacturing process is performed under high pressure, it is difficult to apply the process to industrial mass production.
본 발명에서는 m-아미노페놀을 출발물질로 하여 BBA를 제조하는 공정에 있어서, m-아미노페놀을 m-디부틸아미노페놀로 알킬화하는 공정에서 상압 조건하에서 염기(base)로서 지금까지 사용된 바 없는 산화마그네슘(MgO) 또는 트리에틸아민을 사용하고, 그리고 유기용매를 사용하지 않으며 다만 산화마그네슘 사용시 물을 용매로 사용하고 트리에틸아민을 사용시는 용매를 전혀 사용하지 않으며, 또한 m-디부틸아미노페놀을 구조식(Ⅰ)로 표시되는 BBA로 전환시키는 공정후 반응 혼합물로부터 목적물을 분리·정제하는 방법으로서 수산화나트륨용액을 사용한 염석효과를 통하여 로다민계 불순물을 완전히 배제시킴으로써 본 발명을 완성하였다.In the present invention, in the step of producing BBA using m-aminophenol as a starting material, the step of alkylating m-aminophenol with m-dibutylaminophenol has not been used as a base under atmospheric pressure Magnesium oxide (MgO) or triethylamine is used, and an organic solvent is not used. However, when magnesium oxide is used, water is used as a solvent, no solvent is used when triethylamine is used, and m-dibutylaminophenol As a method of separating and purifying an object from the reaction mixture after the step of converting it into the BBA represented by the structural formula (I), the rhodamine-based impurities are completely eliminated through a salting-out effect using a sodium hydroxide solution.
본 발명은 a) 다음 구조식(Ⅱ)로 표시되는 m-아미노페놀로부터 다음 구조식(Ⅲ)으로 표시되는 m-디부틸아미노페놀을 제조하는 과정과, b) 구조식(Ⅲ)으로 표시되는 화합물로부터 다음 구조식(Ⅰ)로 표시되는 2-(4-디부틸아미노-2-히드록시벤조일)벤조산을 제조하는 과정으로 이루어진 제조방법에 있어서, 상기 a) 과정은 산화마그네슘 또는 트리에틸아민 존재하에서 구조식(Ⅱ)로 표시되는 m-아미노페놀과 부틸 브로마이드를 반응시키는 것을 그 특징으로 한다.The present invention relates to a process for preparing a) m-dibutylaminophenol represented by the following structural formula (III) from m-aminophenol represented by the following structural formula (II), and b) A process for producing 2- (4-dibutylamino-2-hydroxybenzoyl) benzoic acid represented by the structural formula (I), wherein the process a) is carried out in the presence of magnesium oxide or triethylamine, ) With m-aminophenol and butyl bromide.
이와 같은 본 발명을 더욱 상세히 설명하면 다음과 같다.Hereinafter, the present invention will be described in detail.
본 발명에 따른 제조방법에서는 상기 a)과정에서 제조수율을 향상시키고 반응조건을 온화한 조건(mild condition)으로 유지시키기 위해 알킬화제로서 부틸 브로마이드를 선택하여 사용하고 염기로서 산화마그네슘과 같은 값싼 무기화합물 또는 트리에틸아민을 사용하며, 용매로서 물을 사용하거나 또는 용매를 전혀 사용하지 않고 상압하에서 반응을 수행하므로 별도의 부가적인 장치가 필요없고, 또한 상기 b)공정에서 목적 화합물의 분리·정제 방법으로서 수산화나트륨용액을 이용한 염석(salting out) 효과를 적용시켜 불순물의 함유를 완전히 배제시킨 것에 그 특징이 있다.In the production process according to the present invention, butyl bromide is selectively used as an alkylating agent in order to improve the production yield and maintain the reaction conditions in a mild condition in the process a), and a cheap inorganic compound such as magnesium oxide or tri Ethylamine is used and the reaction is carried out under atmospheric pressure without using any solvent or water as a solvent. Therefore, there is no need for a separate additional device, and in the step b), sodium hydroxide And a salting out effect using a solution is applied to completely eliminate the inclusion of impurities.
상기와 같은 본 발명의 제조방법을 보다 간략히 표기하면 다음 반응식 5와 같다.The production method of the present invention as described above will be described more simply.
[반응식 5][Reaction Scheme 5]
먼저, 상기 구조식(Ⅱ)로 표시되는 m-아미노페놀에 부틸 브로마이드와 염기(base)를 투입하고 환류교반하여 상기 구조식(Ⅲ)으로 표시되는 m-디부틸아미노페놀을 제조한다.First, butyl bromide and base are added to m-aminophenol represented by the above structural formula (II) and refluxed and stirred to prepare m-dibutylaminophenol represented by the above structural formula (III).
이때, 염기로서 산화마그네슘(MgO)을 사용한 경우 반응용매로서 물을 사용하고, 염기로서 트리에틸아민을 사용하는 경우 반응용매를 전혀 사용하지 않아도 좋다. 반응물질의 사용량에 있어서, 출발물질로 사용된 상기 구조식(Ⅱ)로 표시되는 m-아미노페놀 1몰에 대하여 부틸 브로마이드는 2.8~4.0몰, 그리고 염기는 1.1~2.15몰을 사용한다. 그 결과 거의 정량적인 수율로 상기 구조식(Ⅲ)으로 표시되는 m-디부틸아미노페놀을 합성할 수 있었다.At this time, when magnesium oxide (MgO) is used as a base, water is used as a reaction solvent, and when a triethylamine is used as a base, a reaction solvent may not be used at all. As to the amount of the reactant to be used, butyl bromide is used in an amount of 2.8 to 4.0 mol and base is used in an amount of 1.1 to 2.15 mol based on 1 mol of the m-aminophenol represented by the structural formula (II) used as a starting material. As a result, it was possible to synthesize m-dibutylaminophenol represented by the above structural formula (III) in almost quantitative yield.
그리고나서, 상기 구조식(Ⅲ)으로 표시되는 m-디부틸아미노페놀에 무수프탈산을 반응시켜 목적 화합물인 상기 구조식(Ⅰ)로 표시되는 BBA를 제조한다. 이러한 BBA 합성반응은 일종의 친핵성 방향족 치환반응(nucleophilic aromatic substitution)으로서, 구조식(Ⅲ)으로 표시되는 m-디부틸아미노페놀의 1-위치의 벤젠고리가 무수프탈산의 카보닐을 공격함으로써 고리가 열리면서 산(COOH)이 생기게 된다. 이때 m-디부틸아미노페놀의 N-치환기가 반응성을 높이게 된다.Then, m-dibutylaminophenol represented by the above structural formula (III) is reacted with phthalic anhydride to prepare BBA represented by the above-mentioned structural formula (I) which is the object compound. This BBA synthesis reaction is a kind of nucleophilic aromatic substitution in which the benzene ring of the 1-position of the m-dibutylaminophenol represented by formula (III) attacks the carbonyl of the phthalic anhydride, Acid (COOH) is generated. At this time, the N-substituent of m-dibutylaminophenol increases the reactivity.
통상적인 BBA 합성방법에서는 불순물로서 붉은색의 로다민계 화합물이 생성되는데, 이 물질은 BBA를 중간체로 하여 제조된 최종염료의 품질에 상당한 영향을 주게 되므로 BBA 합성시 적절한 반응조건 유지 및 효율적인 정제방법을 채택하여 불순물을 완전히 배제시켜야 한다. 본 발명에서는 수산화나트륨용액 바람직하기로는 10~40% 수산화나트륨용액을 이용한 염석효과로 빨간색이 완전 제거된 순수한 BBA를 얻을 수 있었다.In the conventional BBA synthesis method, a red rhodamine compound is produced as an impurity. Since this material significantly affects the quality of the final dye prepared using BBA as an intermediate, it is necessary to maintain proper reaction conditions and efficiently refine the BBA synthesis It is necessary to completely eliminate the impurities. In the present invention, pure BBA in which red is completely removed by salting-out effect using sodium hydroxide solution, preferably 10 to 40% sodium hydroxide solution, was obtained.
이와 같은 본 발명을 다음의 실시예에 의거하여 더욱 상세히 설명하겠는바, 본 발명이 이에 한정되는 것은 아니다. 또한, 다음의 실시예 및 비교예에서 제조한 각각의 화합물은 NMR, IR, mass 및 녹는점으로서 확인하였다.The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto. In addition, the respective compounds prepared in the following examples and comparative examples were identified as NMR, IR, mass and melting points.
[실시예 1][Example 1]
2구 플라스크에 m-아미노페놀(10.92g, 0.1mol), 산화마그네슘(4.43g, 0.11mol) 및 부틸 브로마이드(42.8ml, 0.4mol)를 넣고 물(50ml)을 투입한 다음, 7시간 환류교반 후 반응을 종결시켰다. 반응용기를 식히고 진공을 이용하여 반응용액을 여과하여 고체를 걸러냈다. 여과된 용액을 분액 깔대기로 옮기고 흔들어서 층 분리한 다음, 유기층을 취하고 진공증류로 미반응 부틸 브로마이드를 회수하였으며, 또한 잔사상태의 m-디부틸아미노페놀 22.1g을 얻었다.(순수 m-디부틸아미노페놀 수율 97%)To the two-necked flask, m-aminophenol (10.92 g, 0.1 mol), magnesium oxide (4.43 g, 0.11 mol) and butyl bromide (42.8 ml, 0.4 mol) were added and water (50 ml) The post-reaction was terminated. The reaction vessel was cooled and the reaction solution was filtered using a vacuum to remove the solid. The filtered solution was transferred to a separatory funnel and shaken to separate layers. The organic layer was separated and the unreacted butyl bromide was recovered by vacuum distillation to obtain 22.1 g of residual m-dibutylaminophenol (pure m-dibutylamino Phenol yield 97%)
2구 플라스크에 무수프탈산(20g, 0.14mol)과 톨루엔(50ml)를 넣고 환류 교반한 다음, 여기에 상기에서 제조한 잔사상태의 m-디부틸아미노페놀(22.1g)이 톨루엔(50ml)에 녹아 있는 용액을 적가하였다. 적가가 완전히 끝난 후, 12시간 동안 환류 교반하였다. 반응용기를 식힌 후, 반응용액에 30% 수산화나트륨용액(50ml)을 30분간 천천히 첨가하면 염(salt)이 생성되는데, 생성된 염을 걸러내고 톨루엔(50ml)으로 씻어주었다. 걸러낸 염을 물(200ml)에 녹인 다음, 여기에 10% 염산용액(60ml)를 천천히 첨가하면 고체가 형성되는데 이 고체는 여과하고 건조하였다. 건조된 BBA를 아세톤(100ml)과 물(80ml)을 사용하여 재결정하여 정제된 BBA 30.0g (전체수율:81.1%)을 얻었다.To the two-necked flask, phthalic anhydride (20 g, 0.14 mol) and toluene (50 ml) were added, and the mixture was refluxed and stirred. Then, 22.1 g of the residue m-dibutylaminophenol prepared above was dissolved in 50 ml of toluene Was added dropwise. After the dropwise addition was complete, the mixture was refluxed for 12 hours. After cooling the reaction vessel, 30% sodium hydroxide solution (50 ml) was slowly added to the reaction solution for 30 minutes to form a salt. The resulting salt was filtered out and washed with toluene (50 ml). The filtered salt was dissolved in water (200 ml), and then a 10% hydrochloric acid solution (60 ml) was added slowly to form a solid which was filtered and dried. The dried BBA was recrystallized using acetone (100 ml) and water (80 ml) to obtain 30.0 g of purified BBA (overall yield: 81.1%).
[실시예 2][Example 2]
2구 플라스크에 m-아미노페놀(10.92g, 0.1mol), 트리에틸아민(30ml, 0.215mol) 및 부틸 브로마이드(30ml, 0.28mol)를 넣고, 4시간 환류교반시킨 후 반응을 종결시켰다. 반응용기에 물(50ml)을 붓고 30분간 교반한 다음, 분액 깔대기로 옮겨 층분리 하였다. 유기층을 취하고 진공증류로 미반응 부틸 브로마이드를 회수하였으며, 또한 잔사상태의 m-디부틸아미노페놀 22.1g을 얻었다.(순수 m-디부틸아미노페놀 수율 95%)M-Aminophenol (10.92 g, 0.1 mol), triethylamine (30 ml, 0.215 mol) and butyl bromide (30 ml, 0.28 mol) were placed in a two-necked flask and refluxed and stirred for 4 hours. Water (50 ml) was poured into the reaction vessel and stirred for 30 minutes, then transferred to a separatory funnel and layered. The organic layer was recovered and unreacted butyl bromide was recovered by vacuum distillation to obtain 22.1 g of residual m-dibutylaminophenol (yield of pure m-dibutylaminophenol: 95%).
2구 플라스크에 무수프탈산(20g, 0.14mol)과 톨루엔(50ml)를 넣고 환류 교반한다음, 여기에 상기에서 벤조한 잔사상태의 m-디부틸아미노페놀(22.1g)이 톨루엔(50ml)에 녹아 있는 용액을 적가하였다. 적가가 완전히 끝난 후, 12시간 동안 환류 교반하였다. 반응용기를 식힌 후, 반응용액에 30% 수산화나트륨용액(50ml)을 30분간 천천히 첨가하면 염(salt)이 생성되는데, 생성된 염을 걸러내고 톨루엔(50ml)으로 씻어주었다. 걸러낸 염을 물(200ml)에 녹인 다음, 여기에 10% 염산용액(60ml)를 천천히 첨가하면 고체가 형성되는데 이 고체는 여과하고 건조하였다. 건조된 BBA를 아세톤(100ml)과 물(80ml)을 사용하여 재결정하여 정제된 BBA 29.0g(전체수율:78.5%)을 얻었다.(20 g, 0.14 mol) and toluene (50 ml) were placed in a two-necked flask, and the mixture was refluxed and stirred. Then, m-dibutylaminophenol (22.1 g) in the form of benzoic acid residue was dissolved in toluene Was added dropwise. After the dropwise addition was complete, the mixture was refluxed for 12 hours. After cooling the reaction vessel, 30% sodium hydroxide solution (50 ml) was slowly added to the reaction solution for 30 minutes to form a salt. The resulting salt was filtered out and washed with toluene (50 ml). The filtered salt was dissolved in water (200 ml), and then a 10% hydrochloric acid solution (60 ml) was added slowly to form a solid which was filtered and dried. The dried BBA was recrystallized using acetone (100 ml) and water (80 ml) to obtain 29.0 g of purified BBA (overall yield: 78.5%).
비교예 1Comparative Example 1
오토클레이브(Autoclave) 장치에 m-아미노페놀(10.92g, 0.1mol), 산화마그네슘(4.43g, 0.11mol) 및 부틸 클로라이드(30ml, 0.3mol)를 넣고 물(50ml)을 투입한 다음, 150℃로 반응온도를 유지한 상태로 10시간 동안 교반하였다. 반응용기를 식히고 전공을 이용하여 반응용액을 여과하여 고체를 걸러냈다. 여과된 용액을 분액 깔대기로 옮기고 흔들어서 층 분리한 다음, 유기층을 취하고 진공증류로 미반응 부틸 클로라이드를 회수하였으며, 또한 잔사상태의 m-디부틸아미노페놀 22.1g 을 얻었다.(순수 m-디부틸아미노페놀 수율 80%)M-Aminophenol (10.92 g, 0.1 mol), magnesium oxide (4.43 g, 0.11 mol) and butyl chloride (30 ml, 0.3 mol) were placed in an autoclave apparatus and water (50 ml) And the mixture was stirred for 10 hours while maintaining the reaction temperature. The reaction vessel was allowed to cool and the reaction solution was filtered using a magnetic field to remove the solid. The filtered solution was transferred to a separatory funnel and shaken to separate layers. The organic layer was separated and the unreacted butyl chloride was recovered by vacuum distillation to obtain 22.1 g of residual m-dibutylaminophenol (pure m-dibutylamino Phenol yield 80%)
비교예 2Comparative Example 2
2구 플라스크에 m-아미노페놀(10.92g, 0.1mol), 트리에틸아민(30ml, 0.215mol) 및 부틸 클로라이드(30ml, 0.28mol)를 넣고, 4시간 환류교반시킨 후 반응을 종결시켰다. 반응용기에 물(50ml)를 붓고 30분간 교반한 다음, 분액 깔대기로 옮겨 층분리 하였다. 유기층을 취하고 진공증류로 미반응 부틸 클로라이드를 회수하였으며, 또한 잔사상태의 m-디부틸아미노페놀을 얻었다.(순수 m-디부틸아미노페놀 수율 50%)M-Aminophenol (10.92 g, 0.1 mol), triethylamine (30 ml, 0.215 mol) and butyl chloride (30 ml, 0.28 mol) were added to a two-necked flask and refluxed and stirred for 4 hours. Water (50 ml) was poured into the reaction vessel and stirred for 30 minutes, then transferred to a separatory funnel and layered. The organic layer was recovered and unreacted butyl chloride was recovered by vacuum distillation to obtain residual m-dibutylaminophenol (yield of pure m-dibutylaminophenol: 50%).
본 발명에 따른 상기 구조식(Ⅰ)로 표시되는 BBA의 제조방법은 별도의 부가적인 장치가 필요없고 제조공정이 간편하여 경제적으로 유리하고 폐수의 양을 대폭 감축시키는 효과를 가지고 있으며, 특히 값싼 산화마그네슘 염기를 사용하는 경우 공업적인 대량생산이 유리한 장점이 있다.The process for producing BBA represented by the structural formula (I) according to the present invention is advantageous in economical efficiency and simplifies the production process, and has an effect of drastically reducing the amount of wastewater. In particular, When a base is used, industrial mass production is advantageous.
Claims (4)
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5965053A (en) * | 1982-10-05 | 1984-04-13 | Shin Nisso Kako Co Ltd | Benzoic acid derivative and its preparation |
| JPS6248654A (en) * | 1985-08-27 | 1987-03-03 | Sumitomo Chem Co Ltd | Production of n-alkylaminophenol compound |
| EP0287277A1 (en) * | 1987-04-09 | 1988-10-19 | Sumitomo Chemical Company, Limited | Production and purification of an N,N-diethylaminophenol |
| JPH0356452A (en) * | 1989-07-25 | 1991-03-12 | Mitsui Toatsu Chem Inc | Benzoic acid derivative and production thereof |
| KR920000698A (en) * | 1990-06-08 | 1992-01-29 | 김인호 | Method for producing N, N-dibutylaminophenols |
| KR920000697A (en) * | 1990-06-08 | 1992-01-29 | 김인호 | Method for preparing 3-dialkylaminophenol |
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- 1996-08-14 KR KR1019960033687A patent/KR19980014628A/en not_active Application Discontinuation
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5965053A (en) * | 1982-10-05 | 1984-04-13 | Shin Nisso Kako Co Ltd | Benzoic acid derivative and its preparation |
| JPS6248654A (en) * | 1985-08-27 | 1987-03-03 | Sumitomo Chem Co Ltd | Production of n-alkylaminophenol compound |
| EP0287277A1 (en) * | 1987-04-09 | 1988-10-19 | Sumitomo Chemical Company, Limited | Production and purification of an N,N-diethylaminophenol |
| JPH0356452A (en) * | 1989-07-25 | 1991-03-12 | Mitsui Toatsu Chem Inc | Benzoic acid derivative and production thereof |
| KR920000698A (en) * | 1990-06-08 | 1992-01-29 | 김인호 | Method for producing N, N-dibutylaminophenols |
| KR920000697A (en) * | 1990-06-08 | 1992-01-29 | 김인호 | Method for preparing 3-dialkylaminophenol |
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