KR20000031444A - Process for producing for cinnamic derivetives - Google Patents
Process for producing for cinnamic derivetives Download PDFInfo
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- KR20000031444A KR20000031444A KR1019980047496A KR19980047496A KR20000031444A KR 20000031444 A KR20000031444 A KR 20000031444A KR 1019980047496 A KR1019980047496 A KR 1019980047496A KR 19980047496 A KR19980047496 A KR 19980047496A KR 20000031444 A KR20000031444 A KR 20000031444A
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- C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
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- C07C57/44—Cinnamic acid
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Abstract
Description
본 발명은 신남산 유도체의 제조방법에 관한 것으로, 더욱 상세하게는 가격이 저렴한 원료물질을 사용하면서도 반응 공정이 간단하여 공업적으로 쉽게 이용할 수 있는 화학식 1의 신남산 유도체의 제조방법에 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, which uses an inexpensive raw material and can be easily used industrially due to a simple reaction process.
식중 R은 수소원자 또는 메톡시기를 나타낸다.Wherein R represents a hydrogen atom or a methoxy group.
신남산(계피산)은 발삼나무, 봉선화, 코카잎에 존재하는 물질로서 향수산업에 중요하게 사용되는 중간체이며, 이 물질의 메틸이나 에틸에스테르 유도체가 특히 향수에 많이 사용된다. 한편, 메톡시신남산은 신나메이트계 자외선 흡수제의 중요한 중간체가 된다.Cinnamic acid (cinnamic acid) is an intermediate that is important in the fragrance industry as a substance present in balsam, balsam, and coca leaves, and methyl or ethyl ester derivatives of this substance are particularly used in perfumes. On the other hand, methoxycinnamic acid becomes an important intermediate of the cinnamate ultraviolet absorber.
신남산을 만드는 종래의 제조방법으로는 방향족 알데히드를 출발물질로 하여 피리딘/피페리딘 촉매하에서 말론산과 반응시켜 신남산을 만드는 방법이 있다(미국 특허 2,734,904(1956);J. Am. Chem. Soc., 376(1976)). 그러나 이 방법은 크뇌베나겔(Knoevenagel) 축합반응이라고도 하는데, 반응성이 뛰어나고 높은 수율로 얻어지는데 비하여 원료로 사용되는 말론산의 가격이 비싸서 공업적으로 생산하는데 경제적이지 못하다는 문제점이 있다.Conventional methods for making cinnamic acid include a method of producing cinnamic acid by reacting with malonic acid under a pyridine / piperidine catalyst using aromatic aldehyde as a starting material (US Pat. No. 2,734,904 (1956); J. Am. Chem. Soc , 376 (1976). However, this method is also referred to as Knoevenagel condensation reaction, and has a problem in that it is not economical for industrial production due to the high price of malonic acid used as a raw material as compared with excellent reactivity and high yield.
또 다른 방법으로는 오래 전부터 알려져 왔던 방법으로서 페르킨(Perkin) 반응이라고도 하는데 이 방법은 알데히드와 무수 아세트산을 아세트산 나트륨이나 아세트산 칼륨 촉매 존재하에서 축합반응을 통하여 만든다(Beilstein, Kuhlberg, Ann. 163, 123(1872); Vogels Textbook of Prac. Org. Chem. 5th Ed., 1038). 그러나 이 방법은 반응이 느리고 반응성이 떨어져서 수율이 낮고 그에 따라 수반되는 정제공정이 어려운 단점이 있다.Another method, which has been known for a long time, is also called Perkin reaction. This method produces aldehyde and acetic anhydride through condensation reaction in the presence of sodium acetate or potassium acetate catalyst (Beilstein, Kuhlberg, Ann. 163, 123). (1872); Vogels Textbook of Prac. Org.Chem. 5th Ed., 1038). However, this method has a disadvantage in that the reaction is slow and the reactivity is low, and thus the purification process is difficult.
본 발명의 목적은 상기와 같은 공지 기술의 단점을 개선하고, 값싼 원료물질을 사용하면서도 반응공정이 간단하고 공업적으로 쉽게 이용할 수 있는 신남산 유도체의 제조방법을 제공하는 것이다.It is an object of the present invention to improve the disadvantages of the known techniques as described above, and to provide a process for the preparation of cinnamic acid derivatives in which the reaction process is simple and industrially easy to use while using inexpensive raw materials.
본 발명자들은 상기의 목적을 달성하기 위하여 연구한 거듭한 결과, p-브로모벤젠 유도체를 출발물질로 하여 신남산 유도체를 높은 수율로 제조할 수 있는 본 발명을 완성하게 되었다.The present inventors have studied to achieve the above object, and as a result, the present invention has been able to complete the present invention which can produce cinnamic acid derivatives in high yield using p-bromobenzene derivative as a starting material.
본 발명자들은 또한, 본 발명의 촉매로 사용되는 팔라듐 촉매가 희토금속이어서 가격이 매우 높은 점을 감안하여, 팔라듐 금속에 포스핀 형태의 리간드를 결합시켜 반응성을 증가시킨 공지기술을 개량하여 리간드를 킬레이트화 시킴으로써, 촉매의 안정성을 증가시켜 촉매의 사용량을 최소화하였다.The present inventors also chelate the ligand by improving a known technique that increases the reactivity by binding a phosphine-type ligand to the palladium metal in view of the fact that the palladium catalyst used as the catalyst of the present invention is a rare earth metal and the price is very high. By increasing the stability of the catalyst, the amount of catalyst used is minimized.
본 발명은 화학식 2의 p-브로모벤젠 유도체를 화학식 3의 비스디페닐포스피노에탄 염화팔라듐 착체 촉매와 염기의 존재하에서 아크릴산과 반응시켜 화학식 1의 신남산 유도체를 제조하는 방법에 관한 것이다.The present invention relates to a process for preparing a cinnamic acid derivative of formula (I) by reacting a p-bromobenzene derivative of formula (2) with acrylic acid in the presence of a bisdiphenylphosphinoethane palladium chloride complex catalyst of formula (3) and a base.
(1) (One)
상기 식에서 R은 수소원자 또는 메톡시기를 나타낸다.In the formula, R represents a hydrogen atom or a methoxy group.
본 발명에 따른 제조방법에서 사용가능한 용매로는 물이 바람직하며 화학식 2의 p-브로모벤젠 유도체에 대하여 부피비로 1∼10배를 사용하는 것이 바람직하며, 1∼3배를 사용하는 것이 더욱 바람직하다.As a solvent usable in the production method according to the present invention, water is preferable, and it is preferable to use 1 to 10 times by volume, more preferably 1 to 3 times, based on the p-bromobenzene derivative of the formula (2). Do.
화학식 3의 비스디페닐포스피노에탄 염화팔라듐 착체 촉매는 화학식 2의 p-브로모벤젠 유도체에 대하여 0.5∼0.001 몰퍼센트, 바람직하게는 0.2∼0.01 몰퍼센트를 사용한다.The bisdiphenylphosphinoethane palladium chloride complex catalyst of formula (3) uses 0.5 to 0.001 mole percent, preferably 0.2 to 0.01 mole percent, relative to the p-bromobenzene derivative of formula (2).
아크릴산 역시 화학식 2의 p-브로모벤젠 유도체에 대하여 1.0∼5.0 당량을 사용하는 것이 바람직하며, 1.2∼2.0 당량을 사용하는 것이 더욱 바람직하다.Acrylic acid is also preferably used in an amount of 1.0 to 5.0 equivalents, more preferably 1.2 to 2.0 equivalents, relative to the p-bromobenzene derivative of the formula (2).
또한 염기로서 무수탄산나트륨, 무수탄산칼륨 또는 탄산수소나트륨을 0.5∼3.0 당량을 사용하는 것이 바람직하며, 0.6∼1.5 당량을 사용하는 것이 더욱 바람직하다.In addition, it is preferable to use 0.5-3.0 equivalents of anhydrous sodium carbonate, anhydrous potassium carbonate, or sodium hydrogencarbonate as a base, and it is more preferable to use 0.6-1.5 equivalents.
반응 온도는 80∼160℃가 바람직하며, 100∼140℃가 더욱 바람직하고, 반응 시간은 2∼48시간이 바람직하다.80-160 degreeC is preferable, as for reaction temperature, 100-140 degreeC is more preferable, and reaction time is 2 to 48 hours are preferable.
반응이 완료되면 통상의 방법에 따라 목적 화합물을 분리할 수 있다. 즉, 반응 혼합물을 실온으로 냉각시키고 35% 염산 수용액으로 pH를 5∼6으로 조절하여 생성된 고체를 여과, 건조하여 목적화합물을 얻는다.After the reaction is completed, the target compound can be separated according to a conventional method. That is, the reaction mixture is cooled to room temperature, the pH is adjusted to 5-6 with 35% aqueous hydrochloric acid solution, and the resulting solid is filtered and dried to obtain the target compound.
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 : 신남산의 제조Example 1 Preparation of Cinnamic Acid
1 리터 반응기에 브로모벤젠 157g(1몰), 아크릴산 144g(2몰), 무수탄산나트륨 106g(1몰), 증류수 314g 및 비스디페닐포스피노에탄 염화팔라듐 착체 230mg(0.02몰 퍼센트)을 넣고 내부 온도를 100℃로 승온시켰다. 12 시간 후 내부 온도를 실온으로 냉각시키고 35% 염산 수용액을 가하여 pH를 5로 조절하여 생성된 고체를 여과하였다. 증류수 100㎖로 고체를 세척하고 건조하여 126.54g의 신남산을 얻었다. 분석 결과는 다음과 같다.Into a 1 liter reactor, 157 g (1 mol) of bromobenzene, 144 g (2 mol) of acrylic acid, 106 g (1 mol) of anhydrous sodium carbonate, 314 g of distilled water and 230 mg (0.02 mol percent) of bisdiphenylphosphinoethane palladium chloride complex were added. Was heated to 100 ° C. After 12 hours, the internal temperature was cooled to room temperature and the resulting solid was filtered by adjusting the pH to 5 by adding 35% aqueous hydrochloric acid solution. The solid was washed with 100 ml of distilled water and dried to obtain 126.54 g of cinnamic acid. The analysis results are as follows.
외관: 흰색의 고체Appearance: white solid
녹는점: 133∼135℃Melting Point: 133 ~ 135 ℃
1H NMR(δ): 6.5∼8.3(7H, Ar-CH=CH-), 9.5(1H, -COOH)1 H NMR (δ): 6.5 to 8.3 (7H, Ar—CH═CH—), 9.5 (1H, —COOH)
IR(cm-1): 1680(C=O), 1610(C=C)IR (cm -1 ): 1680 (C = O), 1610 (C = C)
실시예 2: 신남산의 제조Example 2: Preparation of Cinnamic Acid
실시예 1에서 염기로서 무수탄산칼륨 138g(1몰)를 사용하여 100℃에서 8시간 반응시키는 것을 제외하고는 실시예 1과 동일한 방법으로 신남산을 130g 얻었다.In Example 1, 130 g of cinnamic acid was obtained in the same manner as in Example 1, except that 138 g (1 mol) of anhydrous potassium carbonate as a base was reacted at 100 ° C for 8 hours.
실시예 3: 신남산의 제조Example 3: Preparation of Cinnamic Acid
실시예 1에서 염기로서 탄산수소나트륨 168g(2몰)를 사용하여 100℃에서 36시간 반응시키는 것을 제외하고는 실시예 1과 동일한 방법으로 신남산을 118.4g 얻었다.118.4 g of cinnamic acid was obtained in the same manner as in Example 1 except that 168 g (2 mol) of sodium bicarbonate was used as a base in Example 1 and reacted at 100 ° C for 36 hours.
실시예 4: 신남산의 제조Example 4: Preparation of Cinnamic Acid
실시예 1에서 염기로서 무수탄산칼륨 138g(1몰)를 사용하여 130℃에서 2시간 반응시키는 것을 제외하고는 실시예 1과 동일한 방법으로 신남산을 131g 얻었다.In Example 1, 131 g of cinnamic acid was obtained in the same manner as in Example 1 except that 138 g (1 mol) of anhydrous potassium carbonate as a base was reacted at 130 ° C for 2 hours.
실시예 5: p-메톡시신남산의 제조Example 5: Preparation of p-methoxycinnamic acid
1 리터 반응기에 p-브로모아니솔 187g(1몰), 아크릴산 144g(2몰), 무수탄산나트륨 106g(1몰), 증류수 374g 및 비스디페닐포스피노에탄 염화팔라듐 착체 230mg(0.02몰 퍼센트)을 넣고 내부 온도를 100℃로 승온시켰다. 12시간 후 내부 온도를 실온으로 냉각시키고 35% 염산 수용액을 가하여 pH를 5로 조절하여 생성된 고체를 여과하였다. 증류수 150㎖로 고체를 세척하고 건조하여 156.54g의 p-메톡시신남산을 얻었다. 분석결과는 다음과 같다.187 g (1 mol) of p-bromoanisole, 144 g (2 mol) of acrylic acid, 106 g (1 mol) of anhydrous sodium carbonate, 374 g of distilled water and 230 mg (0.02 mol percent) of bisdiphenylphosphinoethane palladium chloride complex in a 1 liter reactor It put and heated up internal temperature at 100 degreeC. After 12 hours, the internal temperature was cooled to room temperature and the resulting solid was filtered by adjusting the pH to 5 by adding 35% aqueous hydrochloric acid solution. The solid was washed with 150 ml of distilled water and dried to obtain 156.54 g of p-methoxycinnamic acid. The analysis results are as follows.
외관: 흰색의 고체Appearance: white solid
녹는점: 175∼177℃Melting Point: 175 ~ 177 ℃
1H NMR(δ): 3.8(3H, -OCH3), 6.1∼7.8(6H, Ar-CH=CH-), 9.5(1H, -COOH)1 H NMR (δ): 3.8 (3H, -OCH 3 ), 6.1-7.8 (6H, Ar-CH = CH-), 9.5 (1H, -COOH)
IR(cm-1):1690(C=O), 1610(C=C)IR (cm -1 ): 1690 (C = O), 1610 (C = C)
실시예 6: p-메톡시신남산의 제조Example 6: Preparation of p-methoxycinnamic acid
실시예 5에서 염기로서 무수탄산칼륨 138g(1몰)을 사용하여 100℃에서 10시간 반응시키는 것을 제외하고는 실시예 5와 동일한 방법으로 p-메톡시신남산을 158g 얻었다.In Example 5, 158 g of p-methoxycinnamic acid was obtained in the same manner as in Example 5 except that 138 g (1 mol) of anhydrous potassium carbonate as a base was reacted at 100 ° C for 10 hours.
실시예 7: p-메톡시신남산의 제조Example 7: Preparation of p-methoxycinnamic acid
실시예 5에서 염기로서 탄산수소나트륨 168g(1몰)을 사용하여 100℃에서 48시간 반응시키는 것을 제외하고는 실시예 5와 동일한 방법으로 신남산을 135g 얻었다.135 g of cinnamic acid was obtained in the same manner as in Example 5, except that 168 g (1 mol) of sodium bicarbonate was used as a base in Example 5 and reacted at 100 ° C for 48 hours.
실시예 8: p-메톡시신남산의 제조Example 8: Preparation of p-methoxycinnamic acid
실시예 5에서 염기로서 무수탄산칼륨 138g(1몰)를 사용하여 130℃에서 3시간 반응시키는 것을 제외하고는 실시예 5와 동일한 방법으로 신남산을 165g 얻었다.In Example 5, 165 g of cinnamic acid was obtained in the same manner as in Example 5 except that 138 g (1 mol) of anhydrous potassium carbonate as a base was reacted at 130 ° C for 3 hours.
비교실시예 1: 신남산의 제조Comparative Example 1: Preparation of Cinnamic Acid
플라스크에 벤즈알데히드 21g(0.2몰), 무수아세트산 30g(0.29몰) 및 아세트산칼륨 12g(0.122몰)를 넣고 교반하면서 160℃까지 내부 온도를 승온시키고 1시간 동안 반응시킨 후 170℃에서 추가로 3시간 동안 반응시켰다. 90℃의 물 100㎖에 반응 용액을 투입하였다. 이 혼합 용액을 100℃로 가열하면서 포화 탄산나트륨 수용액을 적가하면서 미반응 벤즈알데히드를 증류로 제거시켰다. 이와 같은 스팀 증류과정을 끝내고 잔류 용액을 거름종이로 여과하여 반응 중 생성된 부생성물을 제거시켰다. 여과된 여액을 진한 염산을 가하여 pH를 5로 조절하고, 이산화탄소 발생이 멈출 때까지 교반한 다음 실온으로 냉각시켜서 석출된 신남산을 여과하였다. 이 여과된 신남산을 증류수 60g과 염산 20g을 혼합한 용액에 넣고 100℃로 가열하여 고체를 완전히 용해시켰다. 이 혼합 용액을 다시 실온으로 냉각시켜 석출된 고체를 여과하고 건조시켜 신남산 89g를 얻었다. 분석 결과는 실시예 1과 동일하였다.Into the flask was added 21 g (0.2 mol) of benzaldehyde, 30 g (0.29 mol) of acetic anhydride and 12 g (0.122 mol) of potassium acetate while raising the internal temperature to 160 ° C. while stirring and reacting for 1 hour, followed by an additional 3 hours at 170 ° C. Reacted. The reaction solution was added to 100 ml of water at 90 ° C. Unreacted benzaldehyde was distilled off while the mixed solution was heated to 100 ° C. and saturated aqueous sodium carbonate solution was added dropwise. After the steam distillation process, the remaining solution was filtered through a filter paper to remove the by-products generated during the reaction. The filtrate was added with concentrated hydrochloric acid to adjust the pH to 5, stirred until carbon dioxide generation ceased, cooled to room temperature, and the precipitated cinnamic acid was filtered. The filtered cinnamic acid was added to a solution mixed with 60 g of distilled water and 20 g of hydrochloric acid, and heated to 100 ° C. to completely dissolve the solid. The mixed solution was again cooled to room temperature, and the precipitated solid was filtered and dried to obtain 89 g of cinnamic acid. The analysis results were the same as in Example 1.
비교실시예 2: p-메톡시신남산의 제조Comparative Example 2: Preparation of p-methoxycinnamic acid
p-아니스알데히드 165g, 말론산 195g, 피리딘 220g 및 피페리딘 3g을 플라스크에 투입하고 90℃로 승온하여 16시간 동안 교반하였다. 반응 용액을 실온으로 냉각시켜 염산 350g와 증류수 300g를 혼합시킨 용액에 투입하였다. 석출된 p-메톡시신남산을 여과하여 얻은 고체를 가성소다 60g을 증류수 2000g에 녹여 넣은 용액에 투입하고 90℃로 승온시켰다. 이 용액에 활성탄 50g를 투입하여 2시간 동아 교반하고 거름종이로 여과하여 활성탄을 제거하였다. 여과된 여액을 실온으로 냉각시키고 5% 염산 수용액으로 pH를 5로 조절하여 석출된 p-메톡시신남산을 여과하였다. 여과된 p-메톡시신남산을 아세트산 500g에 넣고 다시 50g를 투입한 후 90℃로 승온시켜 고체가 완전히 용해되면 거름종이로 활성탄을 여과하여 제거시키고 여액을 실온으로 냉각하여 얻어지는 고체를 여과한 다음 이를 건조시켜 130g의 p-메톡시신남산을 얻었다. 분석결과는 실시예 5의 결과와 동일하였다.165 g of p-anisaldehyde, 195 g of malonic acid, 220 g of pyridine and 3 g of piperidine were added to the flask, and the mixture was heated to 90 ° C and stirred for 16 hours. The reaction solution was cooled to room temperature and charged into a solution in which 350 g of hydrochloric acid and 300 g of distilled water were mixed. The solid obtained by filtering the precipitated p-methoxycinnamic acid was thrown into the solution which melt | dissolved 60 g of caustic soda in 2000 g of distilled water, and it heated up at 90 degreeC. 50 g of activated carbon was added to the solution, stirred for 2 hours, and filtered through a filter paper to remove activated carbon. The filtered filtrate was cooled to room temperature and the precipitated p-methoxycinnamic acid was filtered by adjusting the pH to 5 with 5% aqueous hydrochloric acid solution. The filtered p-methoxycinnamic acid was added to 500 g of acetic acid, 50 g was added again, and the temperature was raised to 90 ° C .. When the solid was completely dissolved, activated carbon was filtered off with a filtering paper to remove the filtrate, and the filtrate was cooled to room temperature. It dried and obtained 130 g of p-methoxycinnamic acid. The analysis results were the same as those in Example 5.
실시예 및 비교예의 결과에서 알 수 있는 바와 같이 본 발명은 저렴한 원료물질을 사용하면서도 반응 공정이 간단하여 공업적으로 쉽게 이용할 수 있는 신남산 유도체의 제조방법을 제공하고, 개량된 팔라듐 촉매를 사용함으로써, 안정성도 증가시켜 촉매 사용량을 최소화하여 가격이 높은 팔라듐 촉매의 사용량을 줄여 경제적인 신남산 유도체의 제조방법을 제공한다.As can be seen from the results of the examples and comparative examples, the present invention provides a method for preparing a cinnamic acid derivative which can be easily used industrially due to a simple reaction process while using an inexpensive raw material, and by using an improved palladium catalyst. In addition, it increases the stability, minimizes the amount of catalyst used to reduce the amount of expensive palladium catalyst provides an economical method for producing cinnamic acid derivatives.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4814489A (en) * | 1987-07-24 | 1989-03-21 | Monsanto Company | Process for the preparation of substituted olefins from unsaturated organic chlorides and olefins |
| US5334750A (en) * | 1992-04-07 | 1994-08-02 | Bayer Aktiengesellschaft | Process for the preparation of cinnamic acid derivatives |
| JPH06211705A (en) * | 1992-09-09 | 1994-08-02 | Hoechst Ag | Production of aromatic-substituted olefin from chloroaromatic compound |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4814489A (en) * | 1987-07-24 | 1989-03-21 | Monsanto Company | Process for the preparation of substituted olefins from unsaturated organic chlorides and olefins |
| US5334750A (en) * | 1992-04-07 | 1994-08-02 | Bayer Aktiengesellschaft | Process for the preparation of cinnamic acid derivatives |
| JPH06211705A (en) * | 1992-09-09 | 1994-08-02 | Hoechst Ag | Production of aromatic-substituted olefin from chloroaromatic compound |
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