KR950000215B1 - Process for preparing 1,4-dihydro pyridin derivatives - Google Patents
Process for preparing 1,4-dihydro pyridin derivatives Download PDFInfo
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- KR950000215B1 KR950000215B1 KR1019920000622A KR920000622A KR950000215B1 KR 950000215 B1 KR950000215 B1 KR 950000215B1 KR 1019920000622 A KR1019920000622 A KR 1019920000622A KR 920000622 A KR920000622 A KR 920000622A KR 950000215 B1 KR950000215 B1 KR 950000215B1
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- C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
- C07D211/04—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D211/80—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members
- C07D211/84—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen directly attached to ring carbon atoms
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- A61K31/395—Heterocyclic compounds having nitrogen as a ring hetero atom, e.g. guanethidine or rifamycins
- A61K31/435—Heterocyclic compounds having nitrogen as a ring hetero atom, e.g. guanethidine or rifamycins having six-membered rings with one nitrogen as the only ring hetero atom
- A61K31/44—Non condensed pyridines; Hydrogenated derivatives thereof
- A61K31/4422—1,4-Dihydropyridines, e.g. nifedipine, nicardipine
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Abstract
Description
본 발명은 혈관 확장작용과 항 고혈압성을 나타내는 다음 일반식(Ⅰ)로 표시되는 비대칭 1, 4-디하이드로 피리딘 유도체의 새로운 제조방법에 관한 것이다.The present invention relates to a novel method for preparing an asymmetric 1,4-dihydropyridine derivative represented by the following general formula (I), which exhibits vasodilation and antihypertensive properties.
상기 식에서, R¹은 니트로기에 의해서 임의로 일 치환된 페닐기를 나타내며, R²와 R³는 서로 상이하며 각각 수소원자이거나, 탄소원자수가 1 내지 4인 저급알킬기 또는 알콕시 에틸기를 나타내고, R⁴와 R5는 서로 같거나 다른 것으로서 각각 수소원자이거나, 탄소원자수가 1 내지 4인 저급알킬기를 나타낸다.Wherein, R¹ represents an phenyl group substituted arbitrarily by groups nitro, R² and R³ are different and are each a hydrogen atom, carbon atom number is 1 to 4 represents a lower alkyl group or an alkoxy group, R⁴ and R 5 are equal to each other, Or other hydrogen atoms, respectively, or lower alkyl group having 1 to 4 carbon atoms.
상기 식(Ⅰ)로 표시되는 화합물은 이미 알려져 있는 공지화합물로서 독일 특허출원 제 2,117,573.5호에서는 알데히드를 β-케도카복실산 에스테르 및 엔 아미노카복실산 에스테르와 반응하여 1단계 공정으로 비대칭 1, 4-디하이드로 피리딘을 제조하는 방법이 기재되어 있다.The compound represented by the above formula (I) is a known compound that is known in the German Patent Application No. 2,117,573.5. Processes for preparing the same are described.
그러나, 이러한 제조방법은 불순물인 대칭 1, 4-디하이드로 피리딘류가 다량 생성되어 순도가 낮을 뿐만 아니라 이들 불순물울 별도로 정제해야 하는 문제점을 가지고 있어서 수율에 있어서도 개선의 여지가 많았다.However, such a production method has a lot of room for improvement in yield because the large amount of symmetrical 1,4-dihydropyridines, which are impurities, are produced and thus the purity is low, and these impurities have to be purified separately.
따라서, 본 발명의 목적은 상기와 같은 문제점을 해결하고 고순도의 비대칭 1, 4-디하이드로 피리딘을 제조하기 위하여 반응 중간체로 제조되는 일리덴-β-케토카복실산 에스테르를 높은 수율로 제조, 분리함으로써 고순도의 비대칭 1, 4-디하이드로 피리딘을 고수율로 제조하는데 있다.Accordingly, an object of the present invention is to solve the above problems and to prepare a high purity of the lydene-β-ketocarboxylic acid ester prepared as a reaction intermediate in order to prepare a high-purity asymmetric 1, 4-dihydropyridine, high purity Asymmetric 1, 4-dihydro pyridine is prepared in high yield.
이하, 본 발명을 상세히 설명하면 다음과 같다.Hereinafter, the present invention will be described in detail.
본 발명은 다음 일반식(Ⅱ)로 표시되는 알데히드화합물을 유기용매, 알콜 수용액 또는 수용성 알콜용매중에서 아민을 포함하는 촉매 존재하에 다음 일반식(Ⅲ)으로 표시되는 케토카르복실산에스테르와 반응시켜서 중간체인 다음 일반식(Ⅳ)로 표시되는 일리덴-β-케토카르복실산 에스테르를 제조하고, 이를 다음 일반식(Ⅴ)의 엔아미노 카르복실산 에스테르와 반응시켜서 상기 일반식(Ⅰ)의 비대칭 1, 4-디하이드록시 피리딘을 제조함에 있어서, 상기 중간체 제조시 사용되는 촉매로서 다음 일반식(A)로 표시되는 디카르복실산을 사용하여 반응시켜서 됨을 특징으로 하는 것이다.The present invention provides an intermediate by reacting an aldehyde compound represented by the following general formula (II) with a ketocarboxylic acid ester represented by the following general formula (III) in the presence of a catalyst containing an amine in an organic solvent, an aqueous alcohol solution or a water-soluble alcohol solvent. Phosphorus Illidene-β-ketocarboxylic acid ester represented by the following general formula (IV) is prepared, and reacted with the enamino carboxylic acid ester of the following general formula (V) to asymmetric 1 of the general formula (I) , 4-dihydroxy pyridine, characterized in that the reaction is carried out using a dicarboxylic acid represented by the following general formula (A) as a catalyst used in the preparation of the intermediate.
상기 식들중에서, R1, R2, R3, R4및 R5는 각각 상기 정의한 바와 같으며, Z는 수소원자 또는 히드록시기이고, m은 0또는 1이며, n은 1 또는 1 내지 4의 정수이다.Wherein R 1 , R 2 , R 3 , R 4 and R 5 are each as defined above, Z is a hydrogen atom or a hydroxyl group, m is 0 or 1, n is an integer of 1 or 1 to 4 to be.
이와 같은 본 발명을 더욱 상세히 설명하면 다음과 같다.Referring to the present invention in more detail as follows.
본 발명은 상기 일반식(Ⅱ)와 (Ⅲ) 화합물을 아민과 상기 일반식(A)의 디카르복실산으로 이루어진 촉매 존재하에 반응시켜서 중간체인 상기 일반식(Ⅳ)를 고수율로 제조하므로써 목적화합물인 상기 일반식(Ⅰ)의 피리딘 유도체를 높은 수율로 얻을 수 있는 새로운 제조방법이다.The present invention is made by reacting the above general formulas (II) and (III) in the presence of a catalyst consisting of an amine and the dicarboxylic acid of the general formula (A) to produce the intermediate of the general formula (IV) in high yield. It is a novel production method which can obtain the pyridine derivative of the said General formula (I) which is a compound in high yield.
이와 같은 본 발명의 방법에서는 촉매제로서 아민과 디카르복실산을 혼합 사용하는 바, 본 발명에서 사용되는 아민으로는 다음 일반식(a)로 표시되는 화합물이나 다음 일반식(b)로 표시되는 지방족 알킬아민 또는 지방족 디알킬아민, 또는 시클로아민, 시클로알킬아민 또는 방향족 알킬아민을 사용할 수 있다.In such a method of the present invention, amine and dicarboxylic acid are mixed and used as a catalyst. As the amine used in the present invention, a compound represented by the following general formula (a) or an aliphatic represented by the following general formula (b) Alkylamines or aliphatic dialkylamines or cycloamines, cycloalkylamines or aromatic alkylamines can be used.
상기 식들중에서 R은 탄소원자수 1 내지 5개의 저급알킬기를 나타내고, X와 Y는 서로 같거나 다른 것으로서 탄소원자수 1 내지 5개의 저급알킬기를 나타낸다.In the above formula, R represents a lower alkyl group having 1 to 5 carbon atoms, and X and Y represent the same or different lower alkyl groups having 1 to 5 carbon atoms.
이러한 아민의 구체적인 예로는 피페리딘, 4-메틸피페리딘, 벤질아민, 디에틸아민 등을 들 수 있다.Specific examples of such amines include piperidine, 4-methylpiperidine, benzylamine, diethylamine, and the like.
상기와 같은 아민화합물과 함께 촉매로 사용되는 디카르복실산으로서는 상기 일반식(A)로 표시되는 화합물이 사용되는 바, 그 구체적인 예로는 숙신산, 아디프산, 말론산, (D, L)-말린산 등을 들 수 있다.As the dicarboxylic acid used as a catalyst together with the amine compound as described above, the compound represented by the above general formula (A) is used, and specific examples thereof include succinic acid, adipic acid, malonic acid, (D, L)- Malic acid etc. are mentioned.
이러한 아민화합물과 디카르복실산은 아민화합물 1몰당 디카르복실산 0.5∼1몰의 비율로 사용하는 것이 바람직하다.It is preferable to use such an amine compound and dicarboxylic acid in the ratio of 0.5-1 mol of dicarboxylic acids per 1 mol of amine compounds.
한편, 본 발명의 전체 촉매사용량은 상기 일반식(Ⅱ)의 알데하이드 화합물 몰당 0.001 내지 1몰의 비율로 사용하며 특히, 0.01 내지 0.2몰을 사용하는 것이 적합하다. 반응은 통상 -5℃ 내지 110℃의 온도에서 행해지며 특히, 5℃에서 4℃의 온도가 적합하다. 이때 촉매의 사용량이 너무 적으면 반응수율이 현저히 저하되며 너무 과량이면 부반응이 생겨나 오히려 수율이 낮아진다. 사용되는 용매로는 유기용매 또는 알콜수용액, 수용성 알콜용매 특히, 메탄올, 에탄올, 이소프로판올과 같은 지방족 알코올류를 사용하는 것이 바람직하다.On the other hand, the total catalyst usage of the present invention is used in a ratio of 0.001 to 1 mol per mole of the aldehyde compound of the general formula (II), in particular, it is suitable to use 0.01 to 0.2 mol. The reaction is usually carried out at a temperature of -5 ° C to 110 ° C, and particularly preferably a temperature of 5 ° C to 4 ° C. At this time, if the amount of the catalyst used is too small, the reaction yield is significantly lowered. If the amount is too large, side reactions occur, but the yield is lowered. As the solvent used, it is preferable to use an organic solvent or an aqueous alcohol solution, a water-soluble alcohol solvent, in particular aliphatic alcohols such as methanol, ethanol and isopropanol.
본 발명에 의해 사용된 아민과 디카복실산 유도체를 촉매로 사용한 결과 일리덴-β-케토카복실산 에스테르를 높은 수율로 얻을 수 있었으며 이로부터 혈관확장작용과 항고혈압성을 나타내는 고순도의 비대칭 1, 4-디하이드로 피리딘 화합물을 제조할 수 있게 된다.As a result of using the amine and the dicarboxylic acid derivative used in the present invention as a catalyst, the yield of iriden-β-ketocarboxylic acid ester was obtained in a high yield, from which the highly purified asymmetric 1, 4-di exhibiting vasodilation and antihypertension Hydropyridine compounds can be prepared.
이하, 본 발명의 제조방법을 실시예에 의해 상세히 설명한다. 그러나, 본 발명이 이들 실시예에서만 한정되는 것은 아니며 본 발명의 권리범위내에서 변경이 가능하다.Hereinafter, the production method of the present invention will be described in detail by way of examples. However, the present invention is not limited only to these examples, and modifications may be made within the scope of the present invention.
[참고예][Reference Example]
50ml의 메탄올에 100g의 메탈아세토 아세테이트를 가하고 이 용액을 0℃로 냉각한 후 22g의 암모니아가스를 주입하였다. 실온으로 올린후 3시간을 교반시키고 다시 0℃로 냉각하여 1시간을 교반한 후 감압 여과하여 건조하면 침상결정형의 79.3g의 메틸 3-아미노크로토네이트가 수득된다.(수율 : 80%).100 g of metal aceto acetate was added to 50 ml of methanol, and the solution was cooled to 0 ° C, and 22 g of ammonia gas was injected. After raising to room temperature, the mixture was stirred for 3 hours, cooled to 0 ° C, stirred for 1 hour, and then filtered and dried under reduced pressure to obtain 79.3 g of methyl 3-aminocrotonate in the form of needles (yield: 80%).
IR(KBr, Cm-1) : 3400, 3300, 1680IR (KBr, Cm -1 ): 3400, 3300, 1680
NMR(CDCl3, δ) : 1.9(3H, s), 3.6(3H, s), 4.5(1H, s)NMR (CDCl 3 , δ): 1.9 (3H, s), 3.6 (3H, s), 4.5 (1H, s)
[실시예]EXAMPLE
2.5ℓ의 이소프로판올중에 700g의 3-니트로벤즈알데하이드와 723.4g의 에틸아세토 아세테이트를 가한후 여기에 27.35g의 숙신산과 19.72g의 피페리딘을 가한다. 실온에서 24시간을 반응시키고 0℃로 냉각하여 1시간을 더 교반한 후 감압여과하고 400ml의 빙냉이소프로판올로 세척한후 건조시키면 1.13kg의 에틸 2-(3'-니트로벤질 리덴)아세톤 아세테이트가 수득된다. 이것의 여액을 감압 농축한후 이소프로판올로 결정화하면 47g이 추가 수득된다.(수율 : 96.5%)To 2.5 l isopropanol is added 700 g of 3-nitrobenzaldehyde and 723.4 g of ethylaceto acetate followed by 27.35 g of succinic acid and 19.72 g of piperidine. After reacting at room temperature for 24 hours, cooling to 0 ° C., stirring for an additional hour, filtration under reduced pressure, washing with 400 ml of ice-cooled isopropanol, and drying yielded 1.13 kg of ethyl 2- (3′-nitrobenzylidene) acetone acetate. do. The filtrate was concentrated under reduced pressure and crystallized with isopropanol to give 47 g (yield: 96.5%).
IR(KBr, Cm-1) : 1750, 1680, 1550IR (KBr, Cm -1 ): 1750, 1680, 1550
NMR(CDCl3, δ) : 1.15∼1.5(3H, t), 2,45(3H, s), 4.2∼4.6(2H, q), 7.5∼8.45(5H, m).NMR (CDCl 3 , δ): 1.15 to 1.5 (3H, t), 2,45 (3H, s), 4.2 to 4.6 (2H, q), 7.5 to 8.45 (5H, m).
[실시예 2]Example 2
520ml의 이소프로판올중에 140g의 3-니트로벤즈알데하이드와 144.7g의 에틸아세토 아세테이트를 가한후 여기에 2,74g을 숙신산과 3.94g의 피페리딘을 가한다. 실온에서 24시간을 반응시킨후 실시예 1과 같은 방법으로 제조하면 234.2g의 실시예 1과 동일한 화합물이 수득된다(수율 : 97%).To 520 ml of isopropanol is added 140 g of 3-nitrobenzaldehyde and 144.7 g of ethylaceto acetate followed by 2,74 g of succinic acid and 3.94 g of piperidine. After reacting for 24 hours at room temperature and preparing in the same manner as in Example 1, 234.2 g of the same compound as in Example 1 was obtained (yield: 97%).
[실시예 3]Example 3
200ml의 이소프로판올중에 56g의 3-니트로벤즈알데하이드와 57.9g의 에틸아세토 아세테이트를 가한후 여기에 1.35g의 아디프란과 1.58g의 피페리딘을 가한다. 실온에서 20시간을 반응시킨후 실시예 1과 같은 방법으로 제조하면 94.7g의 실시예 1과 동일한 화합물이 수득된다(수율 : 97%).In 200 ml of isopropanol, 56 g of 3-nitrobenzaldehyde and 57.9 g of ethylaceto acetate are added, followed by 1.35 g of adifran and 1.58 g of piperidine. After reacting for 20 hours at room temperature and preparing in the same manner as in Example 1, 94.7 g of the same compound as in Example 1 was obtained (yield: 97%).
[실시예 4]Example 4
200ml의 이소프로판올중에 56g의 3-니트로벤즈알데하이드와 57.9g의 에틸아세토 아세테이트를 가한후 여기에 0.96g말론산과 1.58g의 피페리딘을 가한다. 실온에서 24시간을 반응시킨후 실시예 1과 같은 방법으로 제조하면 93.9g의 실시예 1과 동일한 화합물이 수득된다(수율 : 96.4%).In 200 ml of isopropanol, 56 g of 3-nitrobenzaldehyde and 57.9 g of ethylaceto acetate are added, followed by 0.96 g malonic acid and 1.58 g of piperidine. After reacting for 24 hours at room temperature and preparing in the same manner as in Example 1, 93.9 g of the same compound as in Example 1 was obtained (yield: 96.4%).
[실시예 5]Example 5
520ml의 이소프로판올중에 140g의 3-니트로벤즈알데히드와 144.7g의 에틸아세토 아세테이트를 가한후 여기에 2.74g을 숙신산과 4.59g의 4-메틸피페리딘을 가한다. 실온에서 24시간을 반응시킨후 실시예 1과 같은 방법으로 제조하면 233.6g의 실시예 1과 동일한 화합물이 수득된다(수율 : 95.8%).To 520 ml of isopropanol is added 140 g of 3-nitrobenzaldehyde and 144.7 g of ethyl aceto acetate, followed by 2.74 g of succinic acid and 4.59 g of 4-methylpiperidine. After reacting for 24 hours at room temperature to prepare in the same manner as in Example 1, 233.6 g of the same compound as in Example 1 was obtained (yield: 95.8%).
[실시예 6]Example 6
120ml의 이소프로판올중에 20g의 3-니트로벤즈알데하이드와 20.7g의 에틸아세토 아세테이트를 가한후 여기에 0.62gm의 숙신산과 1.13g의 벤질아민을 가한다. 실온에서 24시간을 반응시킨후 실시예 1과 같은 방법으로 제조하면 33.3g의 실시예 1과 동일한 화합물이 수득된다(수율 : 95. 6%).To 120 ml of isopropanol is added 20 g of 3-nitrobenzaldehyde and 20.7 g of ethylaceto acetate followed by 0.62 gm of succinic acid and 1.13 g of benzylamine. After reacting for 24 hours at room temperature and preparing in the same manner as in Example 1, 33.3 g of the same compound as in Example 1 was obtained (yield: 95. 6%).
[실시예 7]Example 7
80ml의 이소프로판올중에 20g의 3-니트로벤즈알데하이드와 20.7g의 에틸아세토 아세테이트를 가한후 여기에 0.53의 (D, L)-말린산과 0.68g의 피페리딘을 가한다. 실온에서 24시간을 반응시킨후 실시예 1과 같은 방법으로 제조하면 33.7g의 실시예 1과 동일한 화합물이 수득된다(수율 : 96.7%).20 g of 3-nitrobenzaldehyde and 20.7 g of ethylaceto acetate are added to 80 ml of isopropanol, followed by 0.53 of (D, L) -malic acid and 0.68 g of piperidine. When reacted for 24 hours at room temperature and prepared in the same manner as in Example 1, 33.7 g of the same compound as in Example 1 was obtained (yield: 96.7%).
[실시예 8]Example 8
120ml의 에탄올중에 20g의 3-니트로벤즈알데하이드와 20.7g의 에틸아세토 아세테이트를 가한후 여기에 0.47g숙신산과 0.58g의 디에틸아민을 가한다. 실온에서 24시간을 반응시킨후 실시예 1과 같은 방법으로 제조하면 33.2g의 실시예 1과 동일한 화합물이 수득된다(수율 : 95.7%).20 g of 3-nitrobenzaldehyde and 20.7 g of ethyl aceto acetate are added to 120 ml of ethanol, followed by 0.47 g of succinic acid and 0.58 g of diethylamine. When reacted for 24 hours at room temperature and prepared in the same manner as in Example 1, 33.2 g of the same compound as in Example 1 was obtained (yield: 95.7%).
[실시예 9]Example 9
200ml의 이소프로판올중에 50g의 3-니트로벤즈알데하이드와 63.6g의 2-메톡시에틸아세토 아세테이트를 가한후 여기에 0.98g의 숙신산과 1.41g의 피페리딘을 가한다. 실온에서 24시간을 반응시킨후 실시예 1과 같은 방법으로 제조하면 93.6g의 2-메톡시에틸 2-(3'-니트로벤질리덴) 아세토아세테이트가 수득된다(수율 : 96.3%).50 g of 3-nitrobenzaldehyde and 63.6 g of 2-methoxyethylaceto acetate are added to 200 ml of isopropanol, followed by 0.98 g of succinic acid and 1.41 g of piperidine. After reacting for 24 hours at room temperature and preparing in the same manner as in Example 1, 93.6 g of 2-methoxyethyl 2- (3'-nitrobenzylidene) acetoacetate was obtained (yield: 96.3%).
IR(KBr, Cm-1) : 1740, 1670, 1540IR (KBr, Cm -1 ): 1740, 1670, 1540
NMR(CDCl3, δ) : 2.45(3H, s), 3.3(3H, s), 3.5∼3.8(2H, t), 4.35∼4.6(23H, t), 7.45∼8.45(5H, m).NMR (CDCl 3 , δ): 2.45 (3H, s), 3.3 (3H, s), 3.5 to 3.8 (2H, t), 4.35 to 4.6 (23H, t), 7.45 to 8.45 (5H, m).
[실시예 10]Example 10
200ml의 클로로포름 중에 50g의 3-니트로벤즈알데하이드와 63.6g의 2-메톡시에틸아세토 아세테이트를 가한후 여기에 0.98g의 숙신산과 1.41g의 피페리딘을 가한다. 실온에서 24시간을 반응시킨후 감압농축하고 150ml의 이소프로판올로 재결정한 다음, 0℃로 냉각하여 1시간을 교반한후 감압여과하고 40ml의 빙냉이소프로판올로 세척한후 건조시키면 83.0g의 실시예 9와 동일한 화합물이 수득되며 이것의 여액을 감압농축한후 이소프로판올로 결정화하면 11.1g의 실시예 9과 동일한 화합물이 수득된다(수율 : 96.9%).50 g of 3-nitrobenzaldehyde and 63.6 g of 2-methoxyethylaceto acetate are added to 200 ml of chloroform, followed by 0.98 g of succinic acid and 1.41 g of piperidine. After reacting at room temperature for 24 hours, the mixture was concentrated under reduced pressure, recrystallized with 150 ml of isopropanol, cooled to 0 ° C., stirred for 1 hour, filtered under reduced pressure, washed with 40 ml of ice-cold isopropanol, and dried. The same compound is obtained, and the filtrate is concentrated under reduced pressure and crystallized with isopropanol to give 11.1 g of the same compound as in Example 9 (yield: 96.9%).
[실시예 11]Example 11
580ml의 이소프로판올중에 158.5g의 에틸 2-(3'-니트로벤질리덴) 아세토아세테이트와 76.2g의 메틸 3-아미노 크로토네이트를 가한후 가온하여 6시간을 비등시킨다. 실온으로 냉각시켜 3시간을 교반시킨후 감압여과하고 100ml의 이소프로판올로 세척한후 건조시키면 209.6g의 2, 6-디메틸-(3'니트로페닐)-1, 4-디하이드로피리딘-3, 5-디카르복실산-3-메틸-5-에틸에스테르가 수득된다(수율 : 96.6%).In 580 ml of isopropanol, 158.5 g of ethyl 2- (3'-nitrobenzylidene) acetoacetate and 76.2 g of methyl 3-amino crotonate are added and warmed to boil for 6 hours. After cooling to room temperature, the mixture was stirred for 3 hours, filtered under reduced pressure, washed with 100 ml of isopropanol, and then dried. 209.6 g of 2, 6-dimethyl- (3'nitrophenyl) -1, 4-dihydropyridine-3, 5- Dicarboxylic acid-3-methyl-5-ethylester is obtained (yield: 96.6%).
IR(KBr, Cm-1) : 3320, 1710, 1660, 1550IR (KBr, Cm -1 ): 3320, 1710, 1660, 1550
NMR(CDCl3, δ) : 1.1∼1.45(3H, t), 2.35(3H, s), 3.8(6H, s), 3.95∼4.4(2H, q), 5.15(1H, s), 6.1(1H, s), 7.25∼8.2(4H, m).NMR (CDCl 3 , δ): 1.1 to 1.45 (3H, t), 2.35 (3H, s), 3.8 (6H, s), 3.95 to 4.4 (2H, q), 5.15 (1H, s), 6.1 (1H , s), 7.25 to 8.2 (4H, m).
순도 : 99.0%이상(HPLC)Purity: 99.0% or more (HPLC)
이동상 : H2O : CH3CN(64 : 36) Column : C18 Mobile phase: H 2 O: CH 3 CN (64: 36) Column: C 18
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| KR1019920000622A KR950000215B1 (en) | 1992-01-17 | 1992-01-17 | Process for preparing 1,4-dihydro pyridin derivatives |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0884375A1 (en) * | 1997-06-05 | 1998-12-16 | The Lubrizol Corporation | Reaction products of substituted carboxylic acylating agents and carboxylic reactants for use in fuels and lubricants |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0884375A1 (en) * | 1997-06-05 | 1998-12-16 | The Lubrizol Corporation | Reaction products of substituted carboxylic acylating agents and carboxylic reactants for use in fuels and lubricants |
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