KR100212490B1 - Method of producing cinnamic acid - Google Patents
Method of producing cinnamic acid Download PDFInfo
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- KR100212490B1 KR100212490B1 KR1019940034167A KR19940034167A KR100212490B1 KR 100212490 B1 KR100212490 B1 KR 100212490B1 KR 1019940034167 A KR1019940034167 A KR 1019940034167A KR 19940034167 A KR19940034167 A KR 19940034167A KR 100212490 B1 KR100212490 B1 KR 100212490B1
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/10—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide
- C07C51/12—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide on an oxygen-containing group in organic compounds, e.g. alcohols
Abstract
본 발명은 다음 구조식 (II)의 화합물을 NaOCH3촉매하에서 다음 구조식(III)의 화합물과 축합반응시켜서 신남산메틸에스테르 유도체를 얻고, 이를 가수분해하여 다음 구조식(I)의 신남산 유도체를 제조하는 방법에 관한 것이다.The present invention condensation reaction of a compound of formula (II) with a compound of formula (III) under a NaOCH 3 catalyst to obtain a cinnamic acid methyl ester derivative, which is hydrolyzed to prepare a cinnamic acid derivative of the following formula (I) It is about a method.
식중, R은 수소원자 또는 메톡시기를 나타낸다.In the formula, R represents a hydrogen atom or a methoxy group.
본 발명에 의해 제공되는 새로운 신남산 유도체의 제조방법은 출발물질이 저렴하며, 반응성이 우수하고 정제공정이 간단한 새로운 경제적인 제조방법이다.The method for preparing a new cinnamic acid derivative provided by the present invention is a new economical production method with low starting materials, excellent reactivity and simple purification process.
Description
본 발명은 아래 구조식(I)의 신남산 유도체의 새로운 제조방법에 관한 것이다.The present invention relates to a novel process for the preparation of cinnamic acid derivatives of formula (I) below.
식중, R은 수소원자 또는 메톡시기를 나타낸다.In the formula, R represents a hydrogen atom or a methoxy group.
신남산(계피산)은 발삼나무, 봉선화, 코카잎에 존재하는 물질이다. 신남산은 향수산업에 중요하게 사용되는 중간체로서 이 물질의 메틸이나 에틸에스테르가 향수에 많이 사용된다. 메톡시신남산은 신나메이트계 자외선 흡수제의 중요한 중간체가 된다.Cinnamic acid (cinnamon) is a substance present in balsam, balsam, and coca leaves. Cinnamic acid is an important intermediate used in the perfume industry. Methyl or ethyl esters of this material are frequently used in perfumes. Methoxycinnamic acid is an important intermediate for cinnamate UV absorbers.
기존의 신남산을 만드는 제조방법은 방향족 알데히드를 출발물질로 하고 피리딘/피페리딘 촉매하에 말론산과 반응시켜 신남산을 만드는 방법이 있다(미국특허 2,734,904(1956); J. Am. Chem. Soc. ,376(1976)).Existing methods for making cinnamic acid include aromatic aldehyde as a starting material and a method of making cinnamic acid by reacting with malonic acid under a pyridine / piperidine catalyst (US Pat. No. 2,734,904 (1956); J. Am. Chem. Soc. , 376 (1976)).
이 방법은 크뇌베나겔(Knoevenagel) 축합반응이라고 하는데 반응성이 뛰어나고 높은 수율이 얻어지는데 비해 원료로 사용되는 말론산의 가격이 높아서 공업적으로 생산하는 데는 경비가 많이든다. 또 다른 방법으로는 오래전부터 알려져 왔던 방법으로서 페르킨(Perkin) 반응이라고도 하는데 이 방법은 알데히드와 무수 아세트산을 아세트산나트륨이나 아세트산 칼륨 촉매하에서 축합을 시켜서 만든다(Beilstein, Kuhlberg, Ann. 163, 123(1872); Vogel's Textbook of Prac. Org. Chem. 5th Ed., 1038). 이 방법으로는 반응이 느리고 반응이 느리고 반응이 떨어져서 수율이 낮고 그에 따라 수반되는 정제공정이 힘든 단점이 있다.This method is called Knoevenagel condensation reaction, which is highly responsive and yields high, whereas the cost of malonic acid used as a raw material is high, which is expensive to produce industrially. Another method, which has been known for a long time, is also called Perkin reaction, which is made by condensation of aldehyde and acetic anhydride under sodium acetate or potassium acetate catalyst (Beilstein, Kuhlberg, Ann. 163, 123 (1872). Vogel's Textbook of Prac. Org.Chem. 5th Ed., 1038). This method has a disadvantage that the reaction is slow, the reaction is slow, the reaction is low, the yield is low, and the purification process accompanying it is difficult.
본 발명에서는 벤즈알데히드 또는 p-아니스알데히드를 출발물질로 하여 강염기인 NaOCH3촉매 존재하에서 신남산 에스테르류를 제조한 후에 가수분해하여 신남산 및 메톡시신남산을 얻는다. 본 발명은 원료비가 말론산에 비해 상대적으로 저렴하면서 크뇌베니겔 반응과 반응성이 유사하고 정제공정이 상대적으로 상당히 간단하여 공업적으로 즉시 이용가능하다는 데 장점이 있다.In the present invention, cinnamic acid and methoxycinnamic acid are obtained by hydrolysis by preparing cinnamic acid esters in the presence of a strong base NaOCH 3 catalyst using benzaldehyde or p-anisaldehyde as a starting material. The present invention has the advantage that the raw material cost is relatively cheap compared to malonic acid, similar in reactivity with kneubenigel reaction, and the purification process is relatively simple, so that it can be immediately used industrially.
이하 본 발명을 상세히 설명하면 다음과 같다.Hereinafter, the present invention will be described in detail.
출발물질은 다음 구조식 (II)의 화합물을 NaOCH3촉매하에서 다음 구조식 (III)의 화합물과 축합반응시켜서 신남산메틸에스테르를 얻는다.The starting material is condensed with a compound of the following formula (II) under a NaOCH 3 catalyst to obtain methyl cinnamic acid ester.
식중, R은 앞에서 정의한 바와 같다.Wherein R is as defined above.
이때, 용매는 사용하지 않거나 메틸알코올을 출발물질에 대해 1-3당량(무게비)으로 사용한다. 시약 사용량은 구조식(III)의 화합물을 구조식(II)의 화합물에 대해 1당량이상, 바람직하게는 1-5당량 사용하고, 촉매로 사용되는 NaOCH3는 출발물질에 대해 반응 몰비로 0.5-5당량, 바람직하게는 1-3당량을 사용한다. 반응이 진행되는 것을 확인한 후에 반응기에 출발물질대비 무게비로 3-8배의 물을 넣은 후 온도 50이상, 바람직하게는 50-100에서 가수분해를 시킨다. 이때, 소요되는 시간은 2-10시간이다. 가수분해 이후에 35% 염산수용액으로 pH를 6 이하로 조절하고 이때 생성된 고체를 여과, 건조하여 목적물을 얻는다.At this time, the solvent is not used or methyl alcohol is used in 1-3 equivalents (weight ratio) based on the starting material. The amount of reagent used is not less than 1 equivalent, preferably 1-5 equivalents of the compound of formula (III) to the compound of formula (II), and NaOCH 3 used as a catalyst is 0.5-5 equivalents in reaction molar ratio with respect to the starting material. Preferably 1-3 equivalents are used. After confirming that the reaction proceeds, add 3-8 times the water to the reactor by weight ratio of the starting material and then the temperature 50 Or more, preferably 50-100 Hydrolysis at At this time, the time required is 2-10 hours. After hydrolysis, the pH is adjusted to 6 or less with 35% aqueous hydrochloric acid solution, and the resulting solid is filtered and dried to obtain the desired product.
본 발명에 의해 제조될 수 있는 상기 구조식(I)의 화합물의 구체적인 예로는 다음과 같은 화합물을 들 수 있다.Specific examples of the compound of formula (I) that may be prepared by the present invention include the following compounds.
이하, 실시예에서 본 발명의 구체적인 제조방법을 상술한다. 이때, 본 발명이 이들 예로만 한정하는 것은 아니다.Hereinafter, the specific manufacturing method of the present invention in detail in the Examples. At this time, the present invention is not limited only to these examples.
[실시예 1]Example 1
2리터의 반응기에 벤즈알데히드106.12g, 메틸아세테이트 222.24g, NaOC H3(30% 메탄올 용액) 360.13g을 넣은 후 내부온도가 40-60가 되도록 유지시키면서 반응시켰다. 반응이 진행된 것을 TLC로 확인한 후에 물을 500투입하고 온도를 80로 승온하고 교반시켰다. 8시간 교반 뒤 상온 이하로 냉각한 후에 35% 염산 수용액을 이용하여 pH5로 만든 후 여과하고 건조하였다. 얻어진 신남산이 무게는 133.3g이었다. 분석결과는 다음과 같다.Into a 2-liter reactor, 106.12 g of benzaldehyde, 222.24 g of methyl acetate, 360.13 g of NaOC H 3 (30% methanol solution) were added and the internal temperature was 40-60. The reaction was carried out while maintaining it to be. After confirming the reaction proceeded by TLC, water was added to 500 Input temperature 80 It heated up and stirred. After stirring for 8 hours, the mixture was cooled to room temperature or lower, and then made to pH 5 using 35% aqueous hydrochloric acid solution, filtered, and dried. The resulting cinnamic acid weighed 133.3 g. The analysis results are as follows.
외관 : 흰색 분말Appearance: White Powder
녹는점 : 133-135 Melting Point: 133-135
NMR 분석결과(δ) : 6.5-8.3(7H, Ar-CH=CH-), 9.5(1H, -COOH, broad)NMR analysis result (δ): 6.5-8.3 (7H, Ar-CH = CH-), 9.5 (1H, -COOH, broad)
IR 분석결과(cm-1) : 1680(C=0), 1610(C=C)IR analysis result (cm -1 ): 1680 (C = 0), 1610 (C = C)
[실시예 2]Example 2
실시예 1에서 용매로서 메틸알코올 400g을 첨가하고 분말 형태의 NaOCH3를 108.02g을 조심스럽게 투입하였다. 그밖에는 실시예 1과 동일하게 반응을 시킨 뒤 정제공정에 있어서도 동일한 형태로 진행하였다. 얻어진 고체의 무게는 125g이었다. 분석 결과는 실시예 1과 동일하다.In Example 1, 400 g of methyl alcohol was added as a solvent, and 108.02 g of NaOCH 3 in powder form was carefully added. Otherwise, the reaction was carried out in the same manner as in Example 1, and then proceeded in the same manner in the purification step. The weight of the obtained solid was 125 g. The analysis results are the same as in Example 1.
[실시예 3]Example 3
p-아니스알데히드를 출발물질로 하여 메틸아세테이트, NaOCH3를 실시예 1과 동일한 형태 및 동일량을 사용하고 동일한 반응공정을 거쳐 메톡시신남산을 만들었다. 이때, 얻어진 고체는 160g이었다. 분석결과는 다음과 같다.Methyl acetate and NaOCH 3 were prepared using the same form and amount as in Example 1 using p-anisaldehyde as a starting material, and methoxycinnamic acid was prepared through the same reaction process. At this time, the obtained solid was 160g. The analysis results are as follows.
외관 : 흰색의 미세분말Appearance: white fine powder
녹는점 : 175-177 Melting Point: 175-177
원소분석결과 : 분자식 C10H10O3, C : 67.3%, H : 5.6%Elemental analysis results: Molecular formula C 10 H 10 O 3 , C: 67.3%, H: 5.6%
NMR분석결과(δ) : 3.8(3H, -OCH3), 6.1-7.8(6H, -Ar-CH=CH-), 9.5(1H, -COOH)NMR analysis result (δ): 3.8 (3H, -OCH 3 ), 6.1-7.8 (6H, -Ar-CH = CH-), 9.5 (1H, -COOH)
IR분석결과(cm-1) : 1690(C=0), 1610(C=C)IR analysis result (cm -1 ): 1690 (C = 0), 1610 (C = C)
[실시예 4]Example 4
p-아니스알데히드를 출발물질로 하는 것 이외에는 실시예 2와 동일한 공정으로 반응을 진행하여 매톡시신남산을 제조하였다. 이때, 얻어진 고체는 150g이었다. 분석결과는 실시예 3과 동일하다.The reaction proceeded in the same manner as in Example 2, except that p-anisaldehyde was used as a starting material, thereby preparing methoxycinnamic acid. At this time, the obtained solid was 150g. The results are the same as in Example 3.
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| KR1019940034167A KR100212490B1 (en) | 1994-12-14 | 1994-12-14 | Method of producing cinnamic acid |
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| KR1019940034167A KR100212490B1 (en) | 1994-12-14 | 1994-12-14 | Method of producing cinnamic acid |
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| KR100212490B1 true KR100212490B1 (en) | 1999-08-02 |
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