KR19990068257A - Manufacturing method of formamidine for sunscreen - Google Patents
Manufacturing method of formamidine for sunscreen Download PDFInfo
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- KR19990068257A KR19990068257A KR1019980029616A KR19980029616A KR19990068257A KR 19990068257 A KR19990068257 A KR 19990068257A KR 1019980029616 A KR1019980029616 A KR 1019980029616A KR 19980029616 A KR19980029616 A KR 19980029616A KR 19990068257 A KR19990068257 A KR 19990068257A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C257/00—Compounds containing carboxyl groups, the doubly-bound oxygen atom of a carboxyl group being replaced by a doubly-bound nitrogen atom, this nitrogen atom not being further bound to an oxygen atom, e.g. imino-ethers, amidines
- C07C257/10—Compounds containing carboxyl groups, the doubly-bound oxygen atom of a carboxyl group being replaced by a doubly-bound nitrogen atom, this nitrogen atom not being further bound to an oxygen atom, e.g. imino-ethers, amidines with replacement of the other oxygen atom of the carboxyl group by nitrogen atoms, e.g. amidines
- C07C257/12—Compounds containing carboxyl groups, the doubly-bound oxygen atom of a carboxyl group being replaced by a doubly-bound nitrogen atom, this nitrogen atom not being further bound to an oxygen atom, e.g. imino-ethers, amidines with replacement of the other oxygen atom of the carboxyl group by nitrogen atoms, e.g. amidines having carbon atoms of amidino groups bound to hydrogen atoms
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D17/00—Separation of liquids, not provided for elsewhere, e.g. by thermal diffusion
- B01D17/02—Separation of non-miscible liquids
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D9/00—Crystallisation
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Abstract
하기한 화학식 1의 자외선 차단제용 포름아미딘의 제조 방법에 관한 것이다. 이 제조 방법은 아미노벤조에이트, 아닐리드, 촉매 및 유기 용매를 혼합하고, 상기 혼합물을 1차 추출하고, 이 추출물에 재결정 용매를 첨가하여 파우더를 생성하고, 생성된 파우더를 유기 용매에 용해한 후 2차 추출하고, 상기 혼합물을 여과하고 증류하는 공정으로 구성된다.It relates to a method for producing formamidine for the sunscreen of formula 1 below. This preparation method mixes aminobenzoate, anilide, catalyst and organic solvent, first extracts the mixture, adds a recrystallized solvent to the extract to produce a powder, and dissolves the resulting powder in an organic solvent, followed by secondary Extraction and filtering and distilling the mixture.
[화학식 1][Formula 1]
(식에서, R1및 R2는 알킬 그룹이고, A는 H, OH 또는 Cl이며, B는 H, 메톡시, 클로린이고 C는 H, Cl, 알킬, 알콕시이다)(Wherein R 1 and R 2 are alkyl groups, A is H, OH or Cl, B is H, methoxy, chlorine and C is H, Cl, alkyl, alkoxy)
Description
[산업상 이용 분야][Industrial use]
본 발명은 자외선 차단제용 포름아미딘의 제조 방법에 관한 것으로서, 상세하게는 고순도의 포름아미딘을 제조할 수 있는 자외선 차단제용 포름아미딘의 제조 방법에 관한 것이다.The present invention relates to a method for producing formamidine for sunscreen, and more particularly, to a method for producing formamidine for sunscreen capable of producing formamidine of high purity.
[종래 기술][Prior art]
자외선은 가시광선의 보라색보다도 더욱 짧은 파장영역의 광선으로, UVC(200∼280㎚), UVB(280∼320㎚) 및 UVA(320∼400㎚)로 구별된다. 태양으로부터 지구에 내리쬐는 자외선은 대기권 상층에 있는 오존층에서 흡수 산란되어 지상까지 도달하는 양은 극히 적다. 그러나 최근 프레온 등에 의하여 오존층이 파괴되면서, 필터 효과가 감소하여 지구에 도달하는 자외선 양이 증가하고 있으며, 이러한 자외선에 피부가 노출되면 피부색이 검게 변하거나 노화가 촉진되는 등 사회 문제가 되고 있을뿐만 아니라 물질의 황변 현상 및 노화를 촉진시키는 원인이 되고 있다.Ultraviolet rays are light rays having a wavelength shorter than that of visible light purple, and are classified into UVC (200-280 nm), UVB (280-320 nm), and UVA (320-400 nm). Ultraviolet rays emitted from the sun to the earth are absorbed and scattered from the ozone layer in the upper atmosphere and reach the ground. However, recently, as the ozone layer is destroyed by freon, the filter effect decreases and the amount of ultraviolet rays reaching the earth is increasing, and when the skin is exposed to such ultraviolet rays, the skin color becomes black or the aging is promoted. It is a cause of promoting yellowing of the substance and aging.
따라서, 이러한 자외선을 흡수하여 자외선을 차단할 수 있는 산업용 자외선 흡수제(Industrial UV Absorber)에 대한 요구가 증가하고 있다. 자외선 흡수제는 흡수하는 파장 범위에 따라 여러 종류의 자외선 흡수제가 사용되고 있다. 이러한 자외선 흡수제로 주로 사용되는 화합물은 화학구조상 벤조페논(Benzophenone), 벤조트리아졸(Benzotriazole), HALS(Hindered Amine Light Stabilzer), 포름아미딘(Formamidine)기를 갖는 화합물이 주로 사용되고 있다. 자외선 흡수제로 사용되는 화합물 중의 이중 결합이 자외선을 흡수한 후 적외선 에너지형태로 전환방출함에 따라, 피부와 자외선이 직접 접촉하는 것을 차단할 수 있다.Accordingly, there is an increasing demand for an industrial UV absorber that can absorb ultraviolet rays and block ultraviolet rays. Various types of ultraviolet absorbers are used depending on the wavelength range of the ultraviolet absorber. As the compound mainly used as the ultraviolet absorber, a compound having benzophenone, benzotriazole, HLS (Hindered Amine Light Stabilzer), and formamidine group is mainly used in chemical structure. As the double bond in the compound used as the ultraviolet absorber absorbs ultraviolet rays and converts them into infrared energy form, the skin and ultraviolet rays can be blocked from direct contact.
이러한 자외선 흡수제는 소량을 사용하여도 효과가 있어야 하며, 자외선을 흡수할 수 있는 파장 영역이 290∼400㎚의 자외선 전역을 흡수할 수 있는 것이 바람직하며, 또한, 열안정성 및 상용성 등이 우수해야 한다. 이러한 물성을 만족시키는 화합물로 포름아미딘계 화합물을 제조하여 사용하고 있다. 그러나 제조되는 화합물의 순도가 낮아, 자외선 차단 효과가 만족할만한 수준에는 이르지 못하고 있다.Such a UV absorber should be effective even when a small amount is used, and it is preferable that a wavelength range capable of absorbing UV rays can absorb the entire UV region of 290 to 400 nm, and also have excellent thermal stability and compatibility. do. Formamidine compounds are prepared and used as compounds that satisfy these physical properties. However, the purity of the compound produced is low, and the UV blocking effect has not reached a satisfactory level.
본 발명은 상기한 문제점을 해결하기 위한 것으로서, 본 발명의 목적은 자외선 차단제용 포름아미딘을 고순도로 제조할 수 있어서, 자외선 차단 효과가 우수한 자외선 차단제용 포름아미딘의 제조 방법을 제공하는 것이다.The present invention has been made to solve the above problems, and an object of the present invention is to provide a high-purity formamidine for sunscreens, to provide a method for producing formamidine for sunscreens excellent in the sunscreen effect.
도 1은 본 발명의 자외선 차단제용 포름아미딘을 제조하는 공정의 순서를 개략적으로 나타낸 공정도Figure 1 is a process diagram schematically showing the sequence of the process for producing formamidine for sunscreen of the present invention
도 2a는 본 발명의 자외선 차단제용 포름아미딘의 자외선 흡수율을 나타낸 그래프.Figure 2a is a graph showing the ultraviolet absorption rate of formamidine for the sunscreen of the present invention.
도 2b는 종래의 자외선 차단제용 벤조트리아졸 유도체의 자외선 흡수율을 나타낸 그래프.Figure 2b is a graph showing the ultraviolet absorption of the conventional benzotriazole derivatives for sunscreen.
도 2c는 종래의 자외선 차단제용 벤조페논 유도체의 자외선 흡수율을 나타낸 그래프Figure 2c is a graph showing the ultraviolet absorption of the conventional benzophenone derivatives for sunscreen
[과제를 해결하기 위한 수단][Means for solving the problem]
상기한 목적을 달성하기 위하여, 본 발명을 아미노벤조에이트(aminobenzoate), 아닐리드(anilide), 촉매 및 용매를 혼합하고; 상기 혼합물을 1차 추출하고; 상기 추출물에 재결정 용매를 첨가하여 파우더를 생성하고; 상기 파우더를 유기 용매에 용해한 후 2차 추출하고; 상기 혼합물을 여과하고 증류하는 공정을 포함하는 하기한 화학식 1의 자외선 차단제용 포름아미딘의 제조방법을 제공한다.In order to achieve the above object, the present invention is a mixture of aminobenzoate, anilide (anilide), a catalyst and a solvent; First extraction of the mixture; Adding a recrystallized solvent to the extract to produce a powder; Dissolving the powder in an organic solvent and then performing secondary extraction; It provides a method for preparing formamidine for the sunscreen of formula 1 including the step of filtering and distilling the mixture.
[화학식 1][Formula 1]
(식에서, R1및 R2는 알킬 그룹이고, A는 H, OH 또는 Cl이며, B는 H, 메톡시, 클로린이고 C는 H, Cl, 알킬, 알콕시이다)(Wherein R 1 and R 2 are alkyl groups, A is H, OH or Cl, B is H, methoxy, chlorine and C is H, Cl, alkyl, alkoxy)
이하 본 발명의 제조 방법을 공정 순서에 따라 나타낸 도 1을 참조로 하여 더욱 상세하게 설명하면 다음과 같다.Hereinafter, the manufacturing method of the present invention will be described in more detail with reference to FIG.
반응 탱크 자켓(Jacket) 등과 같은 제 1 반응 용기에서 아미노벤조에이트, 아닐리드(anilide) 및 용매를 1 : 1 : 2 ∼ 1 : 2 : 4의 몰비로 혼합하고, 이 혼합물에 촉매를 주입한다. 용매로는 톨루엔 또는 클로로포름을 사용할 수 있고, 촉매로는 오염화인(phosphorus pentachloride: PCl5)을 사용할 수 있다. 상기 제 1 반응 용기 주위에 냉각수를 순환시키면서, 상기 혼합물을 약 50℃에서 약 1시간 동안 반응시키면 하기 반응식 1과 같은 반응에 따라 화학식 1의 포름아미딘이 생성된다. 냉각수를 순환시키면, 반응이 급격하게 일어남에 따른 급격한 온도 상승을 방지할 수 있다.In a first reaction vessel such as a reaction tank jacket or the like, aminobenzoate, anilide and a solvent are mixed in a molar ratio of 1: 1: 1-2: 1: 4, and the catalyst is injected into the mixture. Toluene or chloroform may be used as a solvent, and phosphorus pentachloride (PCl 5 ) may be used as a catalyst. When the mixture is reacted at about 50 ° C. for about 1 hour while circulating cooling water around the first reaction vessel, formamidine of formula 1 is produced according to the reaction shown in Scheme 1 below. By circulating the cooling water, it is possible to prevent the sudden rise in temperature due to the rapid reaction.
반응이 완료되면, 초기 생성물(crude)을 샘플링(sampling)한 후, 분석 실험을 실시하여 반응 상태를 확인한다. 이어서, 다음 공정인 추출 공정에서 염기를 첨가함에 따라 온도가 과도하게 증가하는 것을 방지하기 위하여, 초기 생성물을 약 30℃까지 냉각한다. 냉각 공정에서 온도가 너무 낮아지면 초기 생성물이 굳어버릴 수 있어 바람직하지 않다.When the reaction is completed, the initial product (crude) is sampled (sampling), and then carried out an analytical experiment to confirm the reaction state. The initial product is then cooled to about 30 ° C. in order to prevent the temperature from increasing excessively as the base is added in the next extraction process. If the temperature is too low in the cooling process, the initial product may harden, which is undesirable.
[반응식 1]Scheme 1
2) 1차 추출2) primary extraction
23% 수산화나트륨 수용액에 초기 생성물을 서서히 주입하면서, 제 2 반응 용기 주위에 냉각수를 순환시켜 약 50℃가 넘지 않도록 온도를 조절한다. 온도가 50℃를 넘을 경우, 초기 생성물이 수산화나트륨과 반응하기 전에, 분해되므로 바람직하지 않다.While slowly injecting the initial product into a 23% aqueous sodium hydroxide solution, the temperature is controlled so that the cooling water is circulated around the second reaction vessel to not exceed about 50 ° C. If the temperature exceeds 50 ° C., it is not preferable because the initial product decomposes before reacting with sodium hydroxide.
초기 생성물 주입이 완료되면 냉각수 순환을 중지하고 냉각수를 배출한 다음, 상기 제 2 반응 용기 주위에 스팀을 주입하여 반응 용기 내부 온도를 50℃까지 승온하여 1시간 동안 반응시킨다. 반응이 완료되면, 1시간 동안 방치하여, 유기층과 수용액층을 분리한다. 분리가 완료되면, 하부층의 수용액층을 배출하고, 배출용액의 pH가 12 이상인지 확인한다. 하부층 용액을 완전히 배출하여, 알칼리 성분을 완전히 제거한다. 알칼리 성분이 유기층에 잔존할 경우, 다음 공정인 파우더 처리공정에서 역반응이 일어나므로, 유기층의 pH가 중성이 될 때까지 탈이온수(deionized water)로 충분히 세척한다.When the initial product injection is completed, the cooling water circulation is stopped and the cooling water is discharged. Then, steam is injected around the second reaction vessel to raise the temperature inside the reaction vessel to 50 ° C and react for 1 hour. When the reaction is completed, it is left for 1 hour to separate the organic layer and the aqueous layer. When the separation is completed, the aqueous layer of the lower layer is discharged, and check whether the pH of the discharge solution is 12 or more. The bottom layer solution is drained completely to completely remove the alkaline component. When the alkaline component remains in the organic layer, since a reverse reaction occurs in the next powder treatment step, it is sufficiently washed with deionized water until the pH of the organic layer becomes neutral.
3) 파우더 생성3) powder production
얻어진 유기층에 약 2.5몰의 탈이온수를 주입하고, 교반하면서 재결정 용매로 인산 약 1몰을 주입하여 1시간 동안 반응시키면 파우더가 생성된다. 이어서, 생성된 파우더가 함유된 유기층을 원심분리기로 생성된 고형분(solid)인 파우더와 액체(liquid)를 분리한다.About 2.5 moles of deionized water was injected into the obtained organic layer, and about 1 mole of phosphoric acid was added to the recrystallized solvent while stirring to react for 1 hour to form a powder. Subsequently, the organic layer containing the produced powder is separated from the solid powder and liquid produced by the centrifuge.
4) 2차 추출4) secondary extraction
제 3 반응 용기에 탈이온수 약 2몰과 톨루엔 등의 유기 용매 약 2몰을 넣고, 파우더를 반응 탱크에 주입하여 완전하게 용해한다. 이어서, 얻어진 생성물에 5% 수산화나트륨 수용액을 주입하여 pH를 약 9∼10으로 조절하여, 알칼리성이 되게 한다.About 2 mol of deionized water and about 2 mol of organic solvents, such as toluene, are put into a 3rd reaction container, a powder is inject | poured into a reaction tank, and it melt | dissolves completely. Subsequently, 5% aqueous sodium hydroxide solution is injected into the obtained product to adjust the pH to about 9 to 10 to be alkaline.
제 3 반응 탱크 내부 온도를 40℃까지 승온하여 30분간 반응시키고 30분간 방치하여, 유기층과 수용액층을 분리하고 분리된 수용액층을 제거한다. 소량의 물이 탱크 내부에 잔존할 경우 시간이 흐름에 따라 생성물의 분해가 일어날 수 있으므로 물을 완벽하게 분리하여야 한다. 더욱 효과적으로 물을 제거하기 위하여, 흡습제 등의 약품을 사용하여 물을 제거할 수 도 있다.The temperature inside the third reaction tank is raised to 40 ° C, reacted for 30 minutes, left for 30 minutes, the organic layer and the aqueous solution layer are separated, and the separated aqueous solution layer is removed. If a small amount of water remains in the tank, the product may decompose over time, so the water must be completely separated. In order to remove the water more effectively, it is also possible to remove the water using a chemical agent such as a moisture absorbent.
5) 여과5) Filtration
얻어진 유기층을 여과하여 제 4 반응 탱크로 이송한다.The obtained organic layer is filtered and transferred to a fourth reaction tank.
6) 증류6) distillation
여과 공정이 완료되면, 상기 제 4 반응 탱크에 진공펌프를 연결하고 반응탱크 내부 온도를 100℃까지 승온하는 증류 공정에 의해 유기 용매를 제거하여, 노란색의 화합물인 자외선 흡수제를 얻는다.When the filtration step is completed, the organic solvent is removed by a distillation step of connecting a vacuum pump to the fourth reaction tank and raising the temperature of the reaction tank to 100 ° C., thereby obtaining a yellow compound, an ultraviolet absorber.
[실시예]EXAMPLE
이하 본 발명의 바람직한 실시예 및 비교예를 기재한다. 그러나 하기한 실시예는 본 발명의 바람직한 일실시예일뿐 본 발명이 하기한 실시예에 한정되는 것은 아니다.Hereinafter, preferred examples and comparative examples of the present invention are described. However, the following examples are only preferred embodiments of the present invention and the present invention is not limited to the following examples.
(실시예 1)(Example 1)
제 1 반응 탱크 자켓에서 아미노벤조에이트, 아닐리드(anilide) 및 용매를 1 : 1 : 2의 몰비로 혼합하고, 이 혼합물에 촉매로 PCl5를 주입하였다. 상기 제 1 반응 탱크 자켓 주위에 냉각수를 순환시키면서, 이 혼합물을 약 50℃에서 약 1시간 동안 반응시켰다. 반응이 완료되면, 초기 생성물(crude)을 샘플링(sampling)하여, 분석 실험을 실시하여 반응 상태를 확인하였다. 이어서, 초기 생성물을 약 30℃까지 냉각하였다.In the first reaction tank jacket aminobenzoate, anilide and solvent were mixed in a molar ratio of 1: 1: 1 and PCl 5 was injected into the mixture as a catalyst. The mixture was reacted at about 50 ° C. for about 1 hour while circulating cooling water around the first reaction tank jacket. When the reaction was completed, the initial product (crude) was sampled (sample), and the analysis experiment was carried out to confirm the reaction state. The initial product was then cooled to about 30 ° C.
23% 수산화나트륨 수용액에 초기 생성물을 서서히 주입하면서, 제 2 반응 탱크 자켓 주위에 냉각수를 순환시켜 약 50℃가 넘지 않도록 온도를 조절하였다.While slowly injecting the initial product into a 23% aqueous sodium hydroxide solution, the temperature was adjusted to not exceed about 50 ° C. by circulating cooling water around the second reaction tank jacket.
초기 생성물 주입이 완료되면 냉각수 순환을 중지하고 냉각수를 배출한 다음, 스팀을 주입하여 상기 제 2 반응 탱크 내부 온도를 50℃까지 승온하여 반응시켰다.When the initial product injection was completed, the cooling water circulation was stopped, the cooling water was discharged, and steam was injected to react the reaction by raising the temperature of the second reaction tank to 50 ° C.
1시간 동안 반응시킨 후, 1시간 방치를 하여 유기층과 수용액 층을 분리하였다. 분리가 완료되면, 하부층의 수용액층을 완전히 배출하고, 배출용액의 pH가 12 이상인지 확인하였다. 유기층의 pH가 중성이 될 때까지, 유기 용매층을 탈이온(deionized water)로 충분히 세척하였다.After reacting for 1 hour, the mixture was left for 1 hour to separate the organic layer and the aqueous layer. When separation was completed, the aqueous layer of the lower layer was completely discharged, and the pH of the discharge solution was checked to be 12 or more. The organic solvent layer was sufficiently washed with deionized water until the pH of the organic layer became neutral.
얻어진 유기층에 2.5몰의 탈이온수를 주입하고 탱크 교반기를 회전하면서 인산을 1몰 주입하여 1시간 반응을 시켜 파우더를 생성하였다. 이어서, 생성된 파우더를 포함하는 유기층을, 원심분리기를 이용하여 생성된 고형분(solid)인 파우더와 액체(liquid)를 분리하였다.2.5 mol of deionized water was injected into the obtained organic layer, 1 mol of phosphoric acid was injected while rotating a tank stirrer, and it reacted for 1 hour, and powder was produced. Subsequently, the organic layer containing the produced powder was separated using a centrifuge to form a solid powder and a liquid.
제 3 반응 탱크에 탈이온수 2몰과 톨루엔 등의 유기 용매 2몰을 넣고, 파우더를 상기 제 3 반응 탱크에 주입하여 완전하게 용해하였다. 이어서, 얻어진 생성물에 5% 수산화나트륨 수용액을 주입하여 pH를 약 9로 조절하여, 알칼리성이 되게 하였다.2 mol of deionized water and 2 mol of organic solvents, such as toluene, were put into the 3rd reaction tank, and the powder was inject | poured into the said 3rd reaction tank, and it melt | dissolved completely. Subsequently, 5% aqueous sodium hydroxide solution was injected into the obtained product to adjust the pH to about 9, thereby making alkaline.
상기 제 3 반응 탱크 내부 온도를 40℃까지 승온하여 30분간 반응시키고 30분간 방치하여, 유기층과 수용액층을 분리하였다. 분리된 수용액층을 제 3 반응 탱크로부터 분리하여 폐수 탱크로 배출하였다.The temperature inside the third reaction tank was raised to 40 ° C, reacted for 30 minutes, left for 30 minutes, and the organic layer and the aqueous solution layer were separated. The separated aqueous layer was separated from the third reaction tank and discharged into the wastewater tank.
상기 제 3 반응 탱크에 여과기를 연결하여 유기층을 여과한 후, 제 4 반응 탱크로 이송하였다.The organic layer was filtered by connecting a filter to the third reaction tank, and then transferred to the fourth reaction tank.
여과 공정이 완료되면, 상기 제 4 반응 탱크에 진공펌프를 연결하고 상기 제 4 반응 탱크 내부 온도를 100℃까지 승온하는 증류 공정에 의해 톨루엔을 제거하여 노란색의 화합물인 자외선 흡수제용 포름아미딘을 얻었다.After the filtration process was completed, toluene was removed by a distillation process in which a vacuum pump was connected to the fourth reaction tank and the temperature of the fourth reaction tank was raised to 100 ° C., thereby obtaining a yellow compound, formamidine, which is a yellow compound. .
(비교예 1)(Comparative Example 1)
디메틸포름아마이드 50㎖에 용해된 N,N-비스(4-에톡시카보닐페닐)포름아미딘(6.8g, 0.02몰)의 교반 용액에 포타슘 하이드록사이드 2.0g과 디메틸 설페이트 2㎖(0.02몰)을 첨가하였다. 이 용액을 하루밤동안 교반하고 3시간 동안 100℃로 가열하였다. 반응 혼합물을 물 100㎖에 가하고, 침전물을 여과하고 건조하여 고형분을 얻었다. 이 고형분을 벤젠 150㎖에 용해하고, 용해되지 않은 물질은 여과하여 제거하고 여과액을 고형 잔류물로 농축하였다. 이 고형 잔류물을 클로로포름 50㎖에 용해하였다. 잔류하는 고형분을 여과하여 제거하고, 여과액을 농축하여 N,N'-비스(4-에톡시카보닐페닐)-N-메틸포름아미딘을 제조하였다.In a stirred solution of N, N-bis (4-ethoxycarbonylphenyl) formamidine (6.8 g, 0.02 mol) dissolved in 50 ml of dimethylformamide, 2.0 g of potassium hydroxide and 2 ml (0.02 mol) of dimethyl sulfate ) Was added. The solution was stirred overnight and heated to 100 ° C. for 3 hours. The reaction mixture was added to 100 ml of water, and the precipitate was filtered and dried to obtain a solid. This solid was dissolved in 150 ml of benzene, the undissolved material was filtered off and the filtrate was concentrated to a solid residue. This solid residue was dissolved in 50 ml of chloroform. The remaining solid was removed by filtration, and the filtrate was concentrated to prepare N, N'-bis (4-ethoxycarbonylphenyl) -N-methylformamidine.
실시예 1의 방법에 따라 제조된 포름아미드와 종래의 방법으로 제조된 포름아미딘의 순도를 측정하여 그 결과를 하기한 표 1에 나타내었다.The purity of formamide prepared according to the method of Example 1 and formamidine prepared by the conventional method was measured, and the results are shown in Table 1 below.
상기 표 1에 나타낸 것과 같이, 본 발명의 방법으로 제조한 포름아미딘의 순도가 비교예 1의 방법으로 제조한 포름아미딘보다 매우 높음을 알 수 있다. 또한, 자외선 흡수능도 매우 우수함을 알 수 있다.As shown in Table 1, it can be seen that the purity of formamidine prepared by the method of the present invention is much higher than that of formamidine prepared by the method of Comparative Example 1. In addition, it can be seen that the ultraviolet absorption ability is also very excellent.
또한, 상기 실시예 1의 포름아미딘과 종래의 벤조트리아졸 유도체 및 벤조페논 유도체의 자외선 흡수능을 측정하여 도 2a 내지 도 2c에 각각 나타내었다. 도 2a 내지 도 2c에 나타낸 것과 같이, 본 발명의 포름아미딘이 자외선 흡수율이 우수하므로, 자외선 차단 효과가 우수함을 알 수 있다.In addition, the ultraviolet absorption ability of the formamidine, the conventional benzotriazole derivatives and the benzophenone derivatives of Example 1 was measured and shown in FIGS. 2A to 2C, respectively. As shown in Figures 2a to 2c, since the formamidine of the present invention is excellent in the ultraviolet absorption rate, it can be seen that the UV blocking effect is excellent.
상술한 바와 같이, 본 발명의 방법으로 제조된 포름아미딘은 순도가 매우 높고, 자외선 차단능도 우수하므로, 자외선 차단제로 유용하다.As described above, formamidine produced by the method of the present invention is very high in purity and excellent in UV blocking ability, and thus is useful as a sunscreen.
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