KR20000031443A - Process for producing cinnamic acid derivatives by using paladium complex catalyst - Google Patents
Process for producing cinnamic acid derivatives by using paladium complex catalyst Download PDFInfo
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- KR20000031443A KR20000031443A KR1019980047495A KR19980047495A KR20000031443A KR 20000031443 A KR20000031443 A KR 20000031443A KR 1019980047495 A KR1019980047495 A KR 1019980047495A KR 19980047495 A KR19980047495 A KR 19980047495A KR 20000031443 A KR20000031443 A KR 20000031443A
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Abstract
Description
본 발명은 신남산 유도체의 제조방법에 관한 것으로서, 더욱 상세하게는 활성이 강한 팔라듐 복합촉매를 사용하여 화학식 1의 신남산 유도체를 제조하는 방법에 관한 것이다.The present invention relates to a method for preparing a cinnamic acid derivative, and more particularly, to a method for preparing a cinnamic acid derivative of Chemical Formula 1 using an active palladium complex catalyst.
상기 식에서 R1은 탄소수 1 내지 8의 저급 알킬기이며, R2은 수소, 탄소수 1 내지 10의 알킬기 또는 하이드록시 알킬기이다.In the above formula, R 1 is a lower alkyl group having 1 to 8 carbon atoms, and R 2 is hydrogen, an alkyl group having 1 to 10 carbon atoms, or a hydroxy alkyl group.
신남산 유도체는 그의 자외선을 흡수하는 성질을 이용하여 화장품의 자외선 차단제의 원료로서 사용되고 있으며, 이를 제조하기 위한 여러 가지 방법이 보고되어 왔다. 미국특허 제 4,970,332호에 기술된 방법에 따르면 지지체에 결합된 팔라듐 촉매와 트리알킬아민하에서 4-요오도아니솔과 알킬 아크릴레이트를 반응시켜 신남산 유도체를 제조한다.Cinnamic acid derivatives have been used as a raw material for the sunscreen of cosmetics by using its ultraviolet absorbing properties, and various methods for producing the same have been reported. According to the method described in US Pat. No. 4,970,332, cinnamic acid derivatives are prepared by reacting 4-iodoanisole and alkyl acrylate under a palladium catalyst bound to a support and a trialkylamine.
이 제조방법은 하기 반응식 1과 같다.This preparation method is shown in Scheme 1 below.
상기 반응식 1에서 R2는 탄소수 1 내지 10의 알킬기이다.In Scheme 1, R 2 is an alkyl group having 1 to 10 carbon atoms.
이 방법에 따라 신남산 유도체를 제조하는 경우에는 지지체에 결합된 팔라듐 촉매의 촉매 활성이 떨어져 촉매 사용량이 많고 반응시간이 길고 수율이 낮으며, 염기는 트리알킬아민만으로 한정되는 단점이 있다.In the case of preparing cinnamic acid derivatives according to this method, the catalyst activity of the palladium catalyst bound to the support is low, and thus the amount of the catalyst used is high, the reaction time is long, and the yield is low, and the base is limited to only trialkylamine.
또한 미국 특허 제 5,457,226 호에 기재된 신남산 유도체의 제법은 팔라듐 활성 탄소촉매 및 알카노산 암모늄염하에서 4-알콕시할로벤젠을 알킬 아크릴레이트와 반응시키는 것이다.The preparation of cinnamic acid derivatives described in US Pat. No. 5,457,226 is also the reaction of 4-alkoxyhalobenzene with alkyl acrylates under a palladium activated carbon catalyst and an alkanoic acid ammonium salt.
이 제조방법은 하기 반응식 2와 같다.This preparation method is shown in Scheme 2 below.
상기 반응식 2에서 R1은 탄소수 1 내지 8의 저급 알킬기이며, R2는 수소, 탄소수 1 내지 10의 알킬 또는 하이드록시알킬기, R3, R4, R5는 수소, 탄소수 1 내지 10의 알킬기 또는 하이드록시알킬기이다.In Scheme 2, R 1 is a lower alkyl group having 1 to 8 carbon atoms, R 2 is hydrogen, an alkyl or hydroxyalkyl group having 1 to 10 carbon atoms, R 3 , R 4 , R 5 is hydrogen, an alkyl group having 1 to 10 carbon atoms or It is a hydroxyalkyl group.
이 방법에 따라 신남산 유도체를 제조하는 경우에는, 팔라듐 활성 탄소 촉매 하에서의 반응은 반응속도는 빠르나 촉매 사용량이 많아 반응 종결 후 값이 비싼 팔라듐 촉매를 회수하기 위한 까다로운 활성화 공정이 요구된다는 단점이 있다.In the case of preparing cinnamic acid derivatives according to this method, the reaction under a palladium activated carbon catalyst has a high reaction rate, but a high amount of catalyst is required, which requires a difficult activation process for recovering an expensive palladium catalyst after completion of the reaction.
그리고 상기의 두 제조방법 모두 염기로서 암모늄염을 사용하는 데, 이는 목적 화합물의 색상과 순도에 있어서 만족할 만한 결과를 제공하지 못한다. 이러한 이유로 상기의 공지 방법을 산업적으로 이용하는데는 어려움이 많으며 보다 개선된 방법의 개발이 요구되어 왔다.In addition, both preparation methods use ammonium salts as bases, which do not provide satisfactory results in color and purity of the target compound. For this reason, it is difficult to industrially use the above known methods and development of more improved methods has been required.
본 발명은 상기와 같은 종래 기술의 문제점을 해결하기 위한 것으로서, 본 발명의 목적은 팔라듐 촉매를 회수하기 위한 까다로운 활성화 공정이 필요 없으면서도, 반응시간은 짧고, 순도 및 수율은 높은 신남산 유도체를 제조하는 방법을 제공하는 것이다.The present invention is to solve the problems of the prior art as described above, an object of the present invention is to produce a cinnamic acid derivative having a short reaction time, high purity and high yield, even without a demanding activation process for recovering the palladium catalyst To provide a way.
이러한 목적을 달성하기 위하여 본 발명자들은 연구를 거듭한 결과, 활성이 강한 팔라듐복합촉매를 사용함으로써 촉매의 사용량을 극소화하여 팔라듐 촉매 회수에 필요한 공정을 제거할 수 있으며, 또한 반응성이 강하므로 반응시간이 짧고, 무기염기를 염기로 사용함으로서 색상, 순도 및 수율이 높은 신남산 유도체를 제조할 수 있다는 것을 발견하여 본 발명을 완성하였다.In order to achieve this object, the present inventors have conducted extensive research to minimize the amount of catalyst used by using a highly active palladium complex catalyst, thereby eliminating the process required for the recovery of the palladium catalyst, and also having a high reactivity, thus increasing the reaction time. The present invention was completed by discovering that cinnamic acid derivatives having high color, purity, and yield can be prepared by using a short, inorganic base as a base.
본 발명은 화학식 2의 복합촉매와 무기염기 존재하에서 화학식 3의 4-알콕시할로벤젠을 화학식 4의 아크릴산 유도체와 반응시키는 것을 특징으로 하는 화학식 1의 신남산 유도체의 제조방법에 관한 것이다.The present invention relates to a process for the preparation of cinnamic acid derivatives of formula (1), characterized by reacting 4-alkoxyhalobenzene of formula (3) with acrylic acid derivatives of formula (4) in the presence of a complex catalyst of formula (2) and an inorganic base.
(1) (One)
상기 화학식에서 X는 브롬 또는 요오드이고, R1은 수소, 탄소수 1 내지 8의 저급 알킬기이며, R2는 수소, 탄소수 1 내지 10의 알킬기 또는 하이드록시 알킬기이며, R3은 벤젠 또는 톨루엔이다.In the above formula, X is bromine or iodine, R 1 is hydrogen, a lower alkyl group having 1 to 8 carbon atoms, R 2 is hydrogen, an alkyl group having 1 to 10 carbon atoms or a hydroxy alkyl group, and R 3 is benzene or toluene.
본 발명에 따른 제조방법에 사용되는 화학식 4의 아크릴산 유도체는 화학식 3의 4-알콕시할로벤젠 화합물에 대해 0.5∼5.0 당량을 사용하는 것이 바람직하며, 2∼4 당량을 사용하는 것이 더욱 바람직하다. 화학식 4의 아크릴산 유도체의 사용량이 화학식 3의 4-알콕시할로벤젠 화합물에 대해 0.5 당량 미만일 때는 반응성이 떨어지고, 5 당량을 초과할 때에는 부반응이 일어날 수 있다.The acrylic acid derivative of the general formula (4) used in the preparation method according to the present invention preferably uses 0.5 to 5.0 equivalents, more preferably 2 to 4 equivalents, relative to the 4-alkoxyhalobenzene compound of the general formula (3). When the amount of the acrylic acid derivative of the general formula (4) is less than 0.5 equivalents to the 4-alkoxyhalobenzene compound of the general formula (3), the reactivity decreases.
본 발명에 따른 제조방법에 사용되는 무기 염기는 탄산칼륨, 탄산수소칼륨, 탄산나트륨 및 탄산수소나트륨으로 이루어진 군에서 선택되며, 사용량은 화학식 3의 4-알콕시할로벤젠 화합물에 대해 0.5∼5.0 당량을 사용하는 것이 바람직하며, 1 내지 3 당량을 사용하는 것이 더욱 바람직하다. 무기 염기의 사용량이 화학식 2의 4-알콕시할로벤젠 화합물에 대해 0.5 당량 미만일 때는 반응성이 떨어지고, 5 당량을 초과할 때에는 부반응이 일어날 수 있으며 무기 염기 제거에 어려움이 있다.The inorganic base used in the preparation method according to the present invention is selected from the group consisting of potassium carbonate, potassium hydrogen carbonate, sodium carbonate and sodium hydrogen carbonate, the amount of which is 0.5 to 5.0 equivalents based on the 4-alkoxyhalobenzene compound of the formula (3). It is preferable to use, and it is more preferable to use 1-3 equivalents. When the amount of the inorganic base is less than 0.5 equivalent to the 4-alkoxyhalobenzene compound of Formula 2, the reactivity decreases, and when the amount of the inorganic base exceeds 5 equivalents, side reactions may occur and difficulty in removing the inorganic base.
본 발명에 따른 제조방법에 사용되는 화학식 2의 팔라듐 복합 촉매의 사용량은 화학식 3의 4-알콕시할로벤젠 화합물에 대해 10∼100ppm을 사용하는 것이 바람직하며, 30∼50ppm을 사용하는 것이 더욱 바람직하다. 팔라듐 복합촉매의 사용량이 화학식 3의 4-알콕시할로벤젠 화합물에 대해 10ppm 미만일 때는 반응성이 떨어지고, 100ppm을 초과할 때에는 부반응이 일어날 수 있으며, 경제성이 떨어진다.The amount of the palladium complex catalyst of formula (2) used in the preparation method according to the present invention is preferably 10 to 100 ppm, more preferably 30 to 50 ppm relative to the 4-alkoxyhalobenzene compound of formula (3). . When the amount of the palladium complex catalyst used is less than 10 ppm with respect to the 4-alkoxyhalobenzene compound of Formula 3, the reactivity may be decreased, and when the amount of the palladium complex catalyst exceeds 100 ppm, side reactions may occur, and economic efficiency may be low.
본 발명에 따른 제조방법에 사용되는 용매는 디메틸포름아미드, N-메틸피롤리돈 및 물로 이루어진 군에서 선택되며 사용량은 화학식 3의 4-알콕시할로벤젠 화합물에 대해 질량비로 1∼10배를 사용하는 것이 바람직하며, 2∼6배를 사용하는 것이 더욱 바람직하다. 용매의 사용량이 화학식 3의 4-알콕시할로벤젠 화합물에 대해 1배 미만일 때는 부반응이 일어나며, 10배를 초과할 때에는 반응성이 떨어진다.The solvent used in the preparation method according to the present invention is selected from the group consisting of dimethylformamide, N-methylpyrrolidone and water, and the amount of the solvent used is 1 to 10 times by mass relative to the 4-alkoxyhalobenzene compound of the formula (3). It is preferable to use, and it is more preferable to use 2-6 times. When the amount of the solvent used is less than 1 time with respect to the 4-alkoxyhalobenzene compound of the formula (3), a side reaction occurs, and when the amount is more than 10 times, the reactivity is inferior.
본 발명에 따른 제조방법은 반응온도 50∼150℃의 범위에서 반응시간 약 30분 내지 5시간 동안 수행하는 것이 바람직하며, 더욱 바람직하게는 60∼120℃에서 1∼2 시간 동안 수행한다. 상기한 반응온도보다 온도가 낮으면 반응성이 떨어지고, 상기한 반응온도보다 온도가 높으면 부반응이 일어날 수 있으며, 원하지 않은 목적물이 얻어질 수 있다. 또한, 상기한 반응시간보다 시간이 짧으면 반응성이 떨어지고, 상기한 반응시간보다 시간이 길어지면 부반응이 일어날 수 있다.The preparation method according to the invention is preferably carried out for a reaction time of about 30 minutes to 5 hours in the reaction temperature range of 50 to 150 ℃, more preferably at 60 to 120 ℃ for 1 to 2 hours. If the temperature is lower than the reaction temperature, the reactivity is lowered. If the temperature is higher than the reaction temperature, side reactions may occur, and unwanted targets may be obtained. In addition, if the time is shorter than the above reaction time, the reactivity decreases, and if the time is longer than the above reaction time, side reactions may occur.
반응 완결 후 목적물질은 통상의 분리 방법으로 분리할 수 있다. 즉, 4-알콕시할로벤젠 화합물과 아크릴산 유도체의 반응이 완결되면 반응 용액을 추출 및 농축시킨 후, 감압 증류등의 정제 방법을 사용함으로써 생성된 화학식 1의 화합물을 순수한 상태로 수득할 수 있다.After completion of the reaction the target material can be separated by conventional separation methods. That is, when the reaction of the 4-alkoxyhalobenzene compound and the acrylic acid derivative is completed, the reaction solution may be extracted and concentrated, and then the resulting compound of Chemical Formula 1 may be obtained in a pure state by using a purification method such as vacuum distillation.
이하에서 실시예를 들어 본 발명을 상세히 설명하나 하기 실시예에 의하여 본 발명의 범주가 제한되는 것은 아니다.Hereinafter, the present invention will be described in detail with reference to Examples, but the scope of the present invention is not limited by the following Examples.
실시예 1 : 옥틸 4-메톡시 신남산에스테르의 제조Example 1 Preparation of Octyl 4-methoxy Cinnamic Acid Ester
물 300g, 4-브로모아니솔 187.0g, 탄산칼륨 138.2g, 팔라듐 복합촉매(R3=벤젠) 10mg에 2-에틸헥실 아크릴레이트 276.4g을 천천히 적가하였다. 이 용액을 100℃에서 1시간 동안 교반시킨 후 층 분리를 통해 물층을 제거한 후 감압 증류로 무색의 목적물 275.9g을 얻었다. 상기 목적물의 수율은 95%이었으며, GC에 의한 순도는 99%이었다. NMR에 의한 측정 데이터는 다음과 같다.276.4 g of 2-ethylhexyl acrylate was slowly added dropwise to 300 g of water, 187.0 g of 4-bromoanisole, 138.2 g of potassium carbonate, and 10 mg of a palladium complex catalyst (R 3 = benzene). The solution was stirred at 100 ° C. for 1 hour, and then the water layer was removed by layer separation. Then, 275.9 g of a colorless target product was obtained by distillation under reduced pressure. The yield of the target product was 95%, the purity by GC was 99%. Measurement data by NMR is as follows.
1H-NMR(CDCl3, 400MHZ, ppm): 0.86-0.98(6H, m), 1.25-1.72(9H, m),1 H-NMR (CDCl 3 , 400 MHZ, ppm): 0.86-0.98 (6H, m), 1.25-1.72 (9H, m),
3.84(3H, s), 4.11(2H, d), 6.85-6.95(1H, m), 7.44-7.54(1H, m),3.84 (3H, s), 4.11 (2H, d), 6.85-6.95 (1H, m), 7.44-7.54 (1H, m),
7.64(1H, d)7.64 (1 H, d)
실시예 2 : 옥틸 4-메톡시 신남산에스테르의 제조Example 2 Preparation of Octyl 4-methoxy Cinnamic Acid Ester
물 300g, 4-요도도아니솔 234.0g, 탄산칼륨 138.2g, 팔라듐 복합촉매(R3=벤젠) 10mg에 2-에틸헥실 아크릴레이트 276.4g을 천천히 적가하였다. 이용액을 100℃에서 1시간 동안 교반시킨 후 층 분리를 통해 물층을 제거한 후 감압증류로 무색의 목적물 275.9g을 얻었다. 상기 목적물의 수율은 95%이었으며, GC에 의한 순도는 99.9%이었다. NMR에 의한 측정 데이터는 다음과 같다.276.4 g of 2-ethylhexyl acrylate was slowly added dropwise to 300 g of water, 234.0 g of 4-uridoanisole, 138.2 g of potassium carbonate, and 10 mg of a palladium complex catalyst (R 3 = benzene). The solution was stirred at 100 ° C. for 1 hour, and then the water layer was removed by layer separation. Then, 275.9 g of a colorless target product was obtained by distillation under reduced pressure. The yield of the target product was 95%, purity by GC was 99.9%. Measurement data by NMR is as follows.
1H-NMR(CDCl3, 400MHz, ppm):0.86-0.98(6H, m), 1.25-1.72(9H, m),1 H-NMR (CDCl 3 , 400 MHz, ppm): 0.86-0.98 (6H, m), 1.25-1.72 (9H, m),
3.84(3H, s), 4.11(2H, d), 6.85-6.95(1H, m), 7.44-7.54(1H, m),3.84 (3H, s), 4.11 (2H, d), 6.85-6.95 (1H, m), 7.44-7.54 (1H, m),
7.64(1H, d)7.64 (1 H, d)
실시예 3 : 옥틸 4-메톡시 신남산에스테르의 제조Example 3 Preparation of Octyl 4-methoxy Cinnamic Acid Ester
디메틸포름아미드 300g, 4-브로모아니솔 187.0g, 탄산칼륨 138.2g, 팔라듐 복합촉매(R3=벤젠) 10mg에 2-에틸헥실 아크릴레이트 276.4g을 천천히 적가하였다. 이용액을 100℃에서 1시간 동안 교반시킨 후 층 분리를 통해 물층을 제거한 후 감압증류로 무색의 목적물 275.9g을 얻었다. 상기 목적물의 수율은 95%이었으며, GC에 의한 순도는 99.9%이었다. NMR에 의한 측정 데이터는 다음과 같다.300 g of dimethylformamide, 187.0 g of 4-bromoanisole, 138.2 g of potassium carbonate, and 106.4 mg of palladium complex catalyst (R 3 = benzene) were slowly added dropwise to 276.4 g of 2-ethylhexyl acrylate. The solution was stirred at 100 ° C. for 1 hour, and then the water layer was removed by layer separation. Then, 275.9 g of a colorless target product was obtained by distillation under reduced pressure. The yield of the target product was 95%, purity by GC was 99.9%. Measurement data by NMR is as follows.
1H-NMR(CDCl3, 400MHz, ppm):0.86-0.98(6H, m), 1.25-1.72(9H, m),1 H-NMR (CDCl 3 , 400 MHz, ppm): 0.86-0.98 (6H, m), 1.25-1.72 (9H, m),
3.84(3H, s), 4.11(2H, d), 6.85-6.95(1H, m), 7.44-7.54(1H, m),3.84 (3H, s), 4.11 (2H, d), 6.85-6.95 (1H, m), 7.44-7.54 (1H, m),
7.64(1H, d)7.64 (1 H, d)
비교예 : 옥틸 4-메톡시 신남산에스테르의 제조Comparative Example: Preparation of Octyl 4-methoxy Cinnamic Acid Ester
미국 특허 제 5,457,226 호에 기술된 방법에 따라 4-요오도아니솔 4,68g, 2-에틸헥실아세테이트 4.05g, 트리에틸아민 2.22g, 아세트산 1.32g, 팔라듐 활성 탄소 촉매 15mg을 넣고 150℃에서 3시간 교반한다. 물과 톨루엔을 넣고 충분리 후 2N 염산 용액으로 세척한 후 감압증류하여 수율 80%, GC 순도 95%로 노란색의 목적화합물 4.65g을 얻었다.4,68 g of 4-iodoanisole, 4.05 g of 2-ethylhexyl acetate, 2.22 g of triethylamine, 1.32 g of acetic acid and 15 mg of palladium activated carbon catalyst were added according to the method described in US Pat. No. 5,457,226. Stir for time. After adding enough water and toluene, the mixture was washed with 2N hydrochloric acid solution and distilled under reduced pressure to obtain 4.65 g of a yellow target compound in 80% yield and 95% GC purity.
이상의 실시예 및 비교예에서 확인된 바와 같이 본 발명은 공지의 제조방법보다 공정이 간단하면서도 고순도 및 고수율로 신남산 유도체를 얻을 수 있는 제조방법을 제공한다.As confirmed in the above examples and comparative examples, the present invention provides a method of producing a cinnamic acid derivative with high purity and high yield, while the process is simpler than a known production method.
본 발명은 기존의 방법들과 비교해 볼 때 활성이 강한 팔라듐복합촉매를 사용하여 팔라듐촉매의 사용량을 최소하고, 이에 따라 팔라듐 촉매 회수에 따른 공정이 필요없이 간단한 공정으로 신남산 유도체를 제조할 수 있어 경제성이 우수할 뿐만 아니라, 무기 염기를 사용하여 색상, 순도 및 수율이 높은 신남산 유도체를 제조할 수 있는 방법을 제공한다. 따라서, 본 발명은 자외선 차단제의 성분으로 화장품에 사용되는 유용한 신남산 유도체를 간편하고 경제적으로 제공할 수 있다는 장점이 있다.Compared with the conventional methods, the present invention minimizes the amount of the palladium catalyst by using a highly active palladium complex catalyst, and thus it is possible to prepare cinnamic acid derivatives in a simple process without the need for a palladium catalyst recovery process. In addition to providing excellent economics, the present invention provides a method for preparing cinnamic acid derivatives having high color, purity, and yield using inorganic bases. Therefore, the present invention has the advantage that it is possible to simply and economically provide a useful cinnamic acid derivative used in cosmetics as a component of the sunscreen.
Claims (6)
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1990010617A1 (en) * | 1989-03-09 | 1990-09-20 | Mallinckrodt, Inc. | Process for producing 2-ethylhexyl-p-methoxycinnamate |
| US5187303A (en) * | 1991-04-15 | 1993-02-16 | Imi (Tami) Institute For Research And Development Ltd. | Process for the preparation of octyl methoxy cinnamate |
| US5334750A (en) * | 1992-04-07 | 1994-08-02 | Bayer Aktiengesellschaft | Process for the preparation of cinnamic acid derivatives |
| US5728865A (en) * | 1995-08-24 | 1998-03-17 | Bromine Compounds Ltd. | Process for the preparation of octyl p-methoxy cinnamate |
-
1998
- 1998-11-06 KR KR1019980047495A patent/KR20000031443A/en not_active Application Discontinuation
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1990010617A1 (en) * | 1989-03-09 | 1990-09-20 | Mallinckrodt, Inc. | Process for producing 2-ethylhexyl-p-methoxycinnamate |
| US5187303A (en) * | 1991-04-15 | 1993-02-16 | Imi (Tami) Institute For Research And Development Ltd. | Process for the preparation of octyl methoxy cinnamate |
| US5334750A (en) * | 1992-04-07 | 1994-08-02 | Bayer Aktiengesellschaft | Process for the preparation of cinnamic acid derivatives |
| US5728865A (en) * | 1995-08-24 | 1998-03-17 | Bromine Compounds Ltd. | Process for the preparation of octyl p-methoxy cinnamate |
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