KR100484497B1 - Process for The Preparation of Esters from Olefins - Google Patents

Process for The Preparation of Esters from Olefins Download PDF

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KR100484497B1
KR100484497B1 KR10-2002-0030413A KR20020030413A KR100484497B1 KR 100484497 B1 KR100484497 B1 KR 100484497B1 KR 20020030413 A KR20020030413 A KR 20020030413A KR 100484497 B1 KR100484497 B1 KR 100484497B1
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pyridylalkyl
formate
ester
added
compound
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KR20030092672A (en
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장석복
고상원
나영임
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한국과학기술원
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D213/28—Radicals substituted by singly-bound oxygen or sulphur atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/02—Esters of acyclic saturated monocarboxylic acids having the carboxyl group bound to an acyclic carbon atom or to hydrogen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a chain containing hetero atoms as chain links

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Pyridine Compounds (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

본 발명은 피리딜알킬 포르메이트를 루테니움 착화합물 존재하에서 올레핀과 반응시켜 올레핀에 비하여 탄소가 하나 더 늘어난 에스테르 화합물을 제조하는 방법에 관한 것이다. The present invention relates to a process for the reaction of pyridylalkyl formate with an olefin in the presence of a ruthenium complex to produce an ester compound having one more carbon relative to the olefin.

본 발명에서 사용하는 피리딜알킬 포르메이트를 올레핀에 첨가시켜 피리딜알킬 에스테르를 제조하는 방법은, 하기 화학식(1)의 2-피리딜알킬 포르메이트를 루테니움 착화합물 촉매 존재하에서 올레핀과 반응시켜 하기 화학식(2)의 2-피리딜알킬 에스테르 화합물을 얻는 것을 특징으로 한다. 상기 화학식(1) 및 화학식(2)에서 R은 알킬, 시클로알킬, 알케닐, 시클로알케닐, 알키닐, 아릴 또는 질소, 산소 혹은 황원자를 1개 이상 함유하는 헤테로아릴을 나타내며 n은 탄소수가 0∼3를 나타낸다. 상기 치환체 정의에서 알킬, 알케닐, 또는 알키닐은 바람직하게는 탄소원자 1에서 18개를 함유하며, 바람직하기로는 시클로알킬은 탄소원자 3에서 8까지의 탄소원자를 가질 수 있으며, 시클로알케닐은 바람직하게는 탄소원자 3에서 7개를 함유하고 환상 이중결합을 1개 이상 포함한다. 또한, 아릴은 바람직하게는 페닐 또는 나프틸을 나타내며, 질소, 산소 혹은 황원자를 1개 이상 함유하는 헤테로아릴은 바람직하게는 피리딜, 퓨라닐, 혹은 티에닐을 나타낸다.The method for preparing pyridylalkyl ester by adding pyridylalkyl formate used in the present invention to olefins comprises reacting 2-pyridylalkyl formate of formula (1) with olefin in the presence of a ruthenium complex catalyst It is characterized by obtaining the 2-pyridylalkyl ester compound of the following general formula (2). In formulas (1) and (2), R represents alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, aryl or heteroaryl containing one or more nitrogen, oxygen or sulfur atoms, and n represents 0 carbon atoms. -3 is shown. Alkyl, alkenyl, or alkynyl in the substituent definition preferably contains from 1 to 18 carbon atoms, preferably cycloalkyl may have from 3 to 8 carbon atoms and cycloalkenyl is preferred. Preferably contains 7 to 3 carbon atoms and at least one cyclic double bond. In addition, aryl preferably represents phenyl or naphthyl, and heteroaryl containing one or more nitrogen, oxygen or sulfur atoms preferably represents pyridyl, furanyl or thienyl.

Description

올레핀으로부터 에스테르의 제조방법{Process for The Preparation of Esters from Olefins}Process for The Preparation of Esters from Olefins

본 발명은 올레핀을 루테니움촉매 존재하에 피리딜알킬 포르메이트와 반응시켜 올레핀에 비하여 탄소가 하나 더 늘어난 에스테르를 제조하는 방법에 관한 것이다. The present invention relates to a process for the reaction of olefins with pyridylalkyl formate in the presence of a ruthenium catalyst to produce esters having one more carbon relative to olefins.

에스테르 화합물은 많은 천연물에서 매우 중요한 구성성분이며 의약, 농약 및 섬유산업에서 중간체로 빈번히 사용된다. 석유산업으로부터 저렴하게 대량으로 얻을 수 있는 올레핀을 전이금속을 촉매로 사용하여 에스테르 화합물로 변환시키는 제법은 경제성 및 환경친화성을 고려할 때 실용성이 매우 큰 프로세스이다. Ester compounds are very important constituents in many natural products and are frequently used as intermediates in the pharmaceutical, agrochemical and textile industries. The process of converting olefins, which can be obtained in large quantities inexpensively from the petroleum industry, into a ester compound using a transition metal as a catalyst is a very practical process considering economical and environmental friendliness.

올레핀으로부터 탄소수가 하나 더 늘어난 에스테르의 제조는 기존의 유기반응제법으로는 반응스텝이 긴 과정을 거쳐야 하므로 실용성이 매우 낮다. 따라서 전이금속을 촉매로 사용하여 한 단계를 거쳐 원하는 에스테르를 제공할 수 있는 촉매방법의 개발에 대한 관심이 높다. The production of esters with one more carbon atoms from olefins is very low in practicality since the conventional organic reaction method requires a long reaction step. Therefore, there is a high interest in the development of a catalyst method that can provide a desired ester in one step using a transition metal as a catalyst.

촉매적 방법에 있어서 가장 중요한 점은 반응조건이 보다 온화하고 편리한 방법을 통하여 수율과 선택성이 뛰어나게 생성물을 제공할 수 있는 전이금속 촉매의 개발에 모아지고 있다. 기존에 개발된 촉매방법은 활성화 된 아실메탈 중간체의 탈카르보닐 반응이 대부분 일어나 원하는 에스테르를 제공하는 대신 중간단계에서 반응이 멈추어 알코올을 높은 비율로 생성시키는 단점을 지니고 있다. 이는 원하는 생성물의 수율을 낮추게 하여 반응의 효율을 감소시키는 주요한 원인을 제공하고 있다. The most important point in the catalytic process is to develop a transition metal catalyst capable of providing a product with excellent yield and selectivity through a milder and more convenient reaction condition. The existing catalyst method has a disadvantage in that the decarbonyl reaction of the activated acyl metal intermediate occurs mostly to produce an alcohol at a high rate by stopping the reaction in the intermediate stage instead of providing a desired ester. This provides a major reason for lowering the yield of the desired product, thereby reducing the efficiency of the reaction.

이러한 단점을 극복하기 위해 대부분의 경우 고압의 일산화탄소 가스 존재하에서 반응을 수행하여 탈카르보닐 경로를 억제시키고 있다. (참조: (a) Keim, W.; Becker, J. J. Mol. Catal. 1989, 54, 95. (b) Lavigne, G.; Lugan, N.; Kalck, P.; Soulie J. M.; Lerouge, O.; Saillard, J. Y.; Halet, J. F. J. Am. Chem. Soc. 1992, 114, 10669. (c) Fabre, S.; Kalck, P.; Lavigne, G. Angew. Chem. Int. Ed. Engl. 1997, 36, 1092. (d) Kondo, T.; Okada, T.; Mitsudo, T.-a. Organometallics 1999, 18, 4123.)In order to overcome this disadvantage, in most cases the reaction is carried out in the presence of a high pressure carbon monoxide gas to suppress the decarbonyl pathway. (A) Keim, W .; Becker, J. J. Mol. Catal . 1989, 54 , 95. (b) Lavigne, G .; Lugan, N .; Kalck, P .; Soulie JM; Lerouge, O .; Saillard, JY; Halet, JF J. Am. Chem. Soc . 1992, 114 , 10669. (c) Fabre, S .; Kalck, P .; Lavigne, G. Angew. Chem. Int.Ed. Engl . 1997, 36, 1092. (d ) Kondo, T .; Okada, T .; Mitsudo, T.-a. Organometallics 1999, 18, 4123.)

시도되는 다른 하나의 방법으로서 포르메이트를 반응기질로 사용하는 대신 일산화탄소와 알코올을 직접 사용하는 반응이 개발되었으나 이러한 방법 역시 낮은 수율과 높지 않은 선택성이 주요한 문제점으로 인식되어지고 있다(참고: (a) Ferguson, S. B.; Alper, H. J. J. Chem. Soc., Chem. Commun. 1984, 1349. (b) Parshall, G. W.; Ittel, S. D. Homogeneous Catalysis; Wiley-Interscience: New York, 1993.).Another attempt was made to develop carbon monoxide and alcohol directly instead of using formate as a reactor, but this method has also been recognized as a major problem with low yield and low selectivity (see (a)). Ferguson, SB; Alper, HJ J. Chem. Soc., Chem. Commun . 1984, 1349. (b) Parshall, GW; Ittel, SD Homogeneous Catalysis ; Wiley-Interscience: New York, 1993.).

본 발명자들은 상기 언급된 바와 같은 여러 가지 문제점을 해결하여 온화한 반응조건에서도 목적하는 에스테르 화합물을 좋은 수득률과 높은 선택성으로 얻을 수 있는 제조방법을 개발하기 위하여 예의 연구하였으며, 그 결과 균일성 루테니움 착화합물을 촉매로 사용하고 피리딜알킬그룹을 지니는 포르메이트를 탄소제공물질로 사용하면 올레핀으로부터 탄소수가 하나 더 늘어난 에스테르를 매우 효율적으로 얻을 수 있음을 발견하고 본 발명을 완성하게 되었다. The present inventors earnestly studied in order to solve various problems as mentioned above, and to develop a method for obtaining a desired ester compound with good yield and high selectivity even under mild reaction conditions, and as a result, uniform ruthenium complex The present invention has been completed by discovering that the use of a formate having a pyridylalkyl group as a catalyst and a carbon donor as a carbon donor can obtain an ester having one more carbon number from an olefin very efficiently.

따라서, 본 발명은 균일성 루테니움 착화합물을 촉매로 사용하고 피리딜알킬 포르메이트와 올레핀을 반응시켜 에스테르 화합물을 제조하는 방법의 제공을 목적으로 한다. Accordingly, an object of the present invention is to provide a method for preparing an ester compound by using a homogeneous ruthenium complex as a catalyst and reacting pyridylalkyl formate with an olefin.

본 발명의 올레핀으로부터 에스테르의 제조방법은 하기 화학식(1)의 피리딜알킬포르메이트를 루테니움 착화합물 촉매 존재하에서 올레핀과 반응시켜 화학식(2)의 피리딜알킬 에스테르화합물을 얻는 것을 특징으로 한다. The method for producing an ester from the olefin of the present invention is characterized in that the pyridylalkyl formate of the formula (1) is reacted with an olefin in the presence of a ruthenium complex catalyst to obtain a pyridylalkyl ester compound of the formula (2).

상기 화학식(1) 및 화학식(2)에서 메틸렌 그룹의 수 n은 0∼3의 정수를 나타내며, R은 알킬, 시클로알킬, 알케닐, 시클로알케닐, 알키닐, 아릴 또는 질소, 산소 혹은 황원자를 1개 이상 함유하는 헤테로아릴을 나타낸다. In the formulas (1) and (2), the number n of methylene groups represents an integer of 0 to 3, and R represents alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, aryl or nitrogen, oxygen or sulfur atom. Heteroaryl containing one or more is shown.

상기 치환체 정의에서 알킬, 알케닐, 또는 알키닐은 바람직하게는 탄소원자 1에서 18개를 함유하며, 시클로알킬은 바람직하기로는 탄소원자 3에서 8까지의 탄소원자를 가질 수 있으며, 시클로알케닐은 바람직하게는 탄소원자 3에서 7개를 함유하고 환상 이중결합을 1개 이상 포함한다. 또한, 아릴은 바람직하게는 페닐 또는 나프틸을 나타내며, 질소, 산소 혹은 황원자를 1개 이상 함유하는 헤테로아릴은 바람직하게는 피리딜, 퓨라닐, 혹은 티에닐을 나타낸다. 또한 루테니움 착화합물은 루테니움에 일산화탄소, 클로라이드, 벤젠등이 결합된 화합물을 나타낸다. Alkyl, alkenyl, or alkynyl in the substituent definition preferably contains from 1 to 18 carbon atoms, cycloalkyl may preferably have from 3 to 8 carbon atoms, and cycloalkenyl is preferred. Preferably contains 7 to 3 carbon atoms and at least one cyclic double bond. In addition, aryl preferably represents phenyl or naphthyl, and heteroaryl containing one or more nitrogen, oxygen or sulfur atoms preferably represents pyridyl, furanyl or thienyl. In addition, the ruthenium complex compound refers to a compound in which carbon monoxide, chloride, benzene and the like are bonded to ruthenium.

본 발명의 올레핀으로터 탄소수가 하나 더 늘어난 에스테르를 제조하는 방법은 하기 반응식 (1)로 간단히 나타낼 수 있으며, n=1을 가정하였을 때 반응식 (1)을 보다 상세히 나타내면 하기 반응식 (2)로 나타낼 수 있다.The method for preparing an ester having one more carbon number from the olefin of the present invention can be represented simply by the following reaction formula (1), and assuming that n = 1, the reaction formula (1) is represented by the following reaction formula (2) Can be.

(1) (One)

상기 반응식(2)에서 리간드를 포함한 루테니움 촉매는 피리딜알킬 포르메이트와의 반응을 통하여 루테니움아실히드리드를 형성시키고 이것이 올레핀에 첨가되어 루테니움알킬아실 중간체가 얻어진후 이의 환원성제거반응을 통하여 원하는 피리딜알킬 에스테르 화합물이 생성된다. In the scheme (2), the ruthenium catalyst including the ligand forms ruthenium acylhydride through the reaction with pyridylalkyl formate, which is added to the olefin to obtain a ruthenium alkylacyl intermediate, and then the reduction thereof is removed. The reaction gives the desired pyridylalkyl ester compound.

본 발명에서 촉매로서 사용하는 루테니움 착화합물은 하기 화학식(3)으로 나타낼 수 있다.The ruthenium complex compound used as a catalyst in the present invention can be represented by the following general formula (3).

Rup(CO)q(X)r 화학식(3)Ru p (CO) q (X) r Formula (3)

상기 화학식(3)에서 X는 클로로 또는 브로모를 의미하고 바람직하기로 p는 1∼4, q는 4∼12, r은 0∼2 사이를 나타내며, 보다 바람직하기로는 p=3, q=12, r=0이다. In the formula (3), X means chloro or bromo, preferably p is 1 to 4, q is 4 to 12, r is 0 to 2, and more preferably p = 3, q = 12, r = 0.

본 발명에서 루테니움 착화합물은 상기 화학식(1)의 피리딜알킬 포르메이트화합물을 기준으로 1∼5몰% 사용할 수 있는데, 보다 바람직하게는 2∼3몰% 사용할 수 있다. 루테니움 착화합물을 피리딜알킬 포르메이트 화합물을 기준으로 1몰% 미만 사용하면 본 발명의 목적물인 에스테르 화합물의 수득률이 감소하는 문제가 있고, 5몰% 초과 사용하면 사용량의 증가에 따른 원하는 에스테르 화합물의 수득률 증대 효과가 나타나지 않아 본 발명에서 촉매인 루테니움 착화합물은 상기 화학식(1)의 피리딜알킬 포르메이트 화합물을 기준으로 1∼5몰% 사용하는 것이 좋다. In the present invention, the ruthenium complex compound may be used in an amount of 1 to 5 mol% based on the pyridylalkyl formate compound of Formula (1), and more preferably 2 to 3 mol%. If the ruthenium complex is less than 1 mol% based on the pyridylalkyl formate compound, there is a problem that the yield of the ester compound, which is the object of the present invention, is reduced. It is preferable to use 1 to 5 mol% of the ruthenium complex compound, which is a catalyst in the present invention, based on the pyridylalkyl formate compound of Formula (1).

올레핀은 피리딜알킬 포르메이트에 비하여 2∼5당량의 과량으로 넣어 주는 것이 가장 바람직한데, 2당량 미만 첨가시에는 반응의 수율이 감소하고 5당량을 초과하는 경우는 사용량의 증가에 따른 에스테르의 수득률 증가가 나타나지 않는다. The olefin is most preferably added in an excess of 2 to 5 equivalents compared to pyridylalkyl formate. When less than 2 equivalents is added, the yield of the reaction decreases, and when the amount exceeds 5 equivalents, the yield of the ester is increased. There is no increase.

본 발명의 올레핀으로부터 에스테르 화합물의 제조시 올레핀, 피리딜알킬 포르메이트, 루테니움 촉매를 용매중에서 반응시켜 사용하는데 본 발명에서 용매는 반응에 악영향을 주지 않는 모든 유기용매를 사용할 수 있으며, 보다 바람직하게는 디메틸포름아미드, 아세토니트릴과 같은 극성용매 혹은 1,2-디클로에탄, 테트라히드로퓨란 등을 사용하는 것이 좋다. In preparing an ester compound from the olefin of the present invention, an olefin, a pyridylalkyl formate, and a ruthenium catalyst are used in a solvent. In the present invention, the solvent may use any organic solvent which does not adversely affect the reaction. Preferably, a polar solvent such as dimethylformamide or acetonitrile, or 1,2-dichloroethane, tetrahydrofuran, or the like may be used.

피리딜알킬 포르메이트 화합물를 유기용매에 용해한 후 이 용액에 루테니움 착화합물 촉매와 올레핀을 첨가한 후 100∼160℃에서 0.5∼24시간 동안 반응시키고유기용매를 제거한 후 남은 반응물을 정제하여 에스테르 화합물을 얻을 수 있다. 상기 반응조건에 있어서, 반응온도가 100℃ 미만에서는 반응시간이 현저히 늘어나는 문제가 있고, 160℃ 초과하면 생성물의 수율이 감소하는 문제가 있으며, 반응시간이 30분 미만에서는 반응이 종결되지 않는 문제가 있고, 24시간 초과하면 생성물이 부반응을 통하여 알코올로 변하는 문제가 있어 반응은 100∼160℃에서 0.5∼24시간 동안 실시하는 것이 좋다.After dissolving the pyridylalkyl formate compound in an organic solvent, a ruthenium complex catalyst and an olefin were added to the solution, and then reacted at 100 to 160 ° C. for 0.5 to 24 hours, and after removing the organic solvent, the remaining reactant was purified to obtain an ester compound. You can get it. In the above reaction conditions, when the reaction temperature is less than 100 ℃ has a problem that the reaction time is significantly increased, if the temperature exceeds 160 ℃ there is a problem that the yield of the product is reduced, the reaction does not terminate when the reaction time is less than 30 minutes In addition, if it exceeds 24 hours, there is a problem that the product turns into alcohol through side reactions, and the reaction is preferably performed at 100 to 160 ° C. for 0.5 to 24 hours.

이하, 본 발명을 하기 실시예에 의거하여 보다 구체적으로 설명한다. 그러나, 이들 실시예는 본 발명에 대한 이해를 돕기 위한 것으로서 이들에 의해 본 발명의 권리범위가 한정되는 것은 아니다.Hereinafter, the present invention will be described in more detail based on the following examples. However, these examples are provided to help the understanding of the present invention, and the scope of the present invention is not limited thereto.

<실시예 1> (2-피리딜메틸)-4,4-디메틸 펜타노에이트 합성Example 1 Synthesis of (2-pyridylmethyl) -4,4-dimethyl pentanoate

5 mL의 바이엘용기에 2-피리딜메틸 포르메이트(548 mg, 4.0 mmol)을 넣고 유기용매로 디메틸포름아미드(2 mL)을 첨가하여 균일한 용액으로 만든 후 트리스루테니움 도데카카르보닐 화합물(128 mg, 5 mol%)와 3,3-디메틸-1-부텐(1.01 g, 12 mmol)을 반응용액에 첨가하였다. 2-pyridylmethyl formate (548 mg, 4.0 mmol) was added to a 5 mL Bayer container, and dimethylformamide (2 mL) was added as an organic solvent to form a homogeneous solution, followed by trisruthenium dodecacarbonyl compound. (128 mg, 5 mol%) and 3,3-dimethyl-1-butene (1.01 g, 12 mmol) were added to the reaction solution.

바이엘을 잘 밀봉한 후 반응용액을 135℃의 온도로 3시간 동안 교반한 다음 유기용매를 감압 건조기로 제거하고 남은 반응 혼합물을 실리카겔 관 크로마토그라피에 의하여 정제하여 (2-피리딜메틸)-4,4-디메틸 펜타노에이트를 98%의 수율로 얻었다.After sealing the vial well, the reaction solution was stirred at a temperature of 135 ° C. for 3 hours, the organic solvent was removed with a reduced pressure dryer, and the remaining reaction mixture was purified by silica gel column chromatography (2-pyridylmethyl) -4, 4-dimethyl pentanoate was obtained in a yield of 98%.

1H NMR (CDCl3, 250 MHz) δ 8.50 (d, 1H, J = 4.4 Hz), 7.61 (td, 1H, J = 7.7, 1.4 Hz), 7.26 (d, 1H, J = 7.7 Hz), 7.13 (m, 1H), 5.14 (s, 2H), 2.30 (m, 2H), 1.52 (m, 2H), 0.81 (s, 9H); 13C NMR(CDCl3, 62.5 MHz) δ 174.4, 156.2, 149.8, 137.1, 123.2, 122.2, 67.1, 38.8, 30.4, 30.3, 29.4; IR (neat) 2959, 2870, 1741, 1595, 1475, 1145, 759 cm-1. 1 H NMR (CDCl 3 , 250 MHz) δ 8.50 (d, 1H, J = 4.4 Hz), 7.61 (td, 1H, J = 7.7, 1.4 Hz), 7.26 (d, 1H, J = 7.7 Hz), 7.13 (m, 1H), 5.14 (s, 2H), 2.30 (m, 2H), 1.52 (m, 2H), 0.81 (s, 9H); 13 C NMR (CDCl 3 , 62.5 MHz) δ 174.4, 156.2, 149.8, 137.1, 123.2, 122.2, 67.1, 38.8, 30.4, 30.3, 29.4; IR (neat) 2959, 2870, 1741, 1595, 1475, 1145, 759 cm -1 .

<실시예 2> 2-피리딜메틸 헵타노에이트 합성Example 2 Synthesis of 2-pyridylmethylheptanoate

5 mL의 바이엘용기에 2-피리딜메틸 포르메이트(548 mg, 4.0 mmol)을 넣고 유기용매로 디메틸포름 아미드(2 mL)을 첨가하여 균일한 용액으로 만든 후 트리스루테니움 도데카카르보닐 화합물(128 mg, 5 mol%)와 1-헥신(1.01 g, 12 mmol)을 반응용액에 첨가하였다. 2-pyridylmethyl formate (548 mg, 4.0 mmol) was added to a 5 mL Bayer container, and dimethylformamide (2 mL) was added as an organic solvent to make a uniform solution, followed by trisruthenium dodecacarbonyl compound. (128 mg, 5 mol%) and 1-hexine (1.01 g, 12 mmol) were added to the reaction solution.

바이엘을 잘 밀봉한 후 반응용액을 135℃의 온도로 3시간 동안 교반한 다음 유기용매를 감압 건조기로 제거하고 남은 반응 혼합물을 실리카겔 관 크로마토그라피에 의하여 정제하여 2-피리딜메틸 헵타노에이트를 73%의 수율로 얻었다. After sealing the vial well, the reaction solution was stirred at a temperature of 135 ° C. for 3 hours, the organic solvent was removed with a vacuum dryer, and the remaining reaction mixture was purified by silica gel column chromatography to obtain 2-pyridylmethyl heptanoate. Obtained in% yield.

1H NMR (CDCl3, 250 MHz) δ 8.60 (d, 1H, J = 4.7 Hz), 7.70 (td, 1H, J = 7.7, 1.8 Hz), 7.35 (d, 1H, J = 7.8 Hz), 7.23 (m, 1H), 5.23 (s, 2H), 2.43 (t, 2H, J = 7.5 Hz), 1.67 (m, 2H), 1.30 (m, 6H), 0.88 (t, 3H, J = 6.6 Hz); 13C NMR (CDCl3, 62.5 MHz) δ 173.5, 156.0, 149.4, 136.7, 122.8, 121.7, 66.6, 34.2, 31.4, 28.8, 24.9, 22.4, 14.0; IR (neat) 2933, 2861, 1741, 1596, 1471, 1164, 914, 732 cm-1. 1 H NMR (CDCl 3 , 250 MHz) δ 8.60 (d, 1H, J = 4.7 Hz), 7.70 (td, 1H, J = 7.7, 1.8 Hz), 7.35 (d, 1H, J = 7.8 Hz), 7.23 (m, 1H), 5.23 (s, 2H), 2.43 (t, 2H, J = 7.5 Hz), 1.67 (m, 2H), 1.30 (m, 6H), 0.88 (t, 3H, J = 6.6 Hz) ; 13 C NMR (CDCl 3 , 62.5 MHz) δ 173.5, 156.0, 149.4, 136.7, 122.8, 121.7, 66.6, 34.2, 31.4, 28.8, 24.9, 22.4, 14.0; IR (neat) 2933, 2861, 1741, 1596, 1471, 1164, 914, 732 cm -1 .

<실시예 3> 2-피리딜메틸-3-시클로헥실 아세테이트 합성Example 3 2-Pyridylmethyl-3-cyclohexyl Acetate Synthesis

5 mL의 바이엘용기에 2-피리딜메틸 포르메이트(548 mg, 4.0 mmol)을 넣고 유기용매로 디메틸포름 아미드(2 mL)을 첨가하여 균일한 용액으로 만든 후 트리스루테니움 도데카카르보닐 화합물(128 mg, 5 mol%)와 시클로헥신(986 mg, 12 mmol)을 반응용액에 첨가하였다. 2-pyridylmethyl formate (548 mg, 4.0 mmol) was added to a 5 mL Bayer container, and dimethylformamide (2 mL) was added as an organic solvent to make a uniform solution, followed by trisruthenium dodecacarbonyl compound. (128 mg, 5 mol%) and cyclohexine (986 mg, 12 mmol) were added to the reaction solution.

바이엘을 잘 밀봉한 후 반응용액을 135℃의 온도로 12시간 동안 교반한 다음 유기용매를 감압 건조기로 제거하고 남은 반응 혼합물을 실리카겔 관 크로마토그라피에 의하여 정제하여 2-피리딜메틸-3-시클로헥실 아세테이트를 87%의 수율로 얻었다.After sealing the vial well, the reaction solution was stirred at a temperature of 135 ° C. for 12 hours, the organic solvent was removed with a reduced pressure dryer, and the remaining reaction mixture was purified by silica gel column chromatography to obtain 2-pyridylmethyl-3-cyclohexyl. Acetate was obtained in 87% yield.

1H NMR (CDCl3, 250 MHz) δ 8.59 (d, 1H, J = 4.8 Hz), 7.70 (td, 1H, J = 7.7, 1.8 Hz), 7.35 (d, 1H, J = 7.8 Hz), 7.22 (m, 1H), 5.23 (s, 2H), 2.45 (t, 2H, J = 7.8 Hz), 1.72-1.53 (m, 7H), 1.25-1.15 (m, 4H), 0.91 (m, 2H); 13C NMR(CDCl3, 62.5 MHz) δ 174.1, 156.3, 149.8, 137.1, 123.2, 122.1, 67.0, 37.5, 33.3, 32.7, 32.2, 26.9, 26.6; IR (neat) 2926, 2853, 1742, 1594, 1448, 1161, 760cm-1. 1 H NMR (CDCl 3 , 250 MHz) δ 8.59 (d, 1H, J = 4.8 Hz), 7.70 (td, 1H, J = 7.7, 1.8 Hz), 7.35 (d, 1H, J = 7.8 Hz), 7.22 (m, 1H), 5.23 (s, 2H), 2.45 (t, 2H, J = 7.8 Hz), 1.72-1.53 (m, 7H), 1.25-1.15 (m, 4H), 0.91 (m, 2H); 13 C NMR (CDCl 3 , 62.5 MHz) δ 174.1, 156.3, 149.8, 137.1, 123.2, 122.1, 67.0, 37.5, 33.3, 32.7, 32.2, 26.9, 26.6; IR (neat) 2926, 2853, 1742, 1594, 1448, 1161, 760 cm -1 .

<실시예 4> 2-피리딜메틸-3-페닐 프로파노에이트 합성Example 4 Synthesis of 2-pyridylmethyl-3-phenyl propanoate

5 mL의 바이엘용기에 2-피리딜메틸 포르메이트(548 mg, 4.0 mmol)을 넣고 유기용매로 디메틸포름 아미드(2 mL)을 첨가하여 균일한 용액으로 만든 후 트리스루테니움 도데카카르보닐 화합물(128 mg, 5 mol%)와 스티렌(1.25 g, 12 mmol)을 반응용액에 첨가하였다. 2-pyridylmethyl formate (548 mg, 4.0 mmol) was added to a 5 mL Bayer container, and dimethylformamide (2 mL) was added as an organic solvent to make a uniform solution, followed by trisruthenium dodecacarbonyl compound. (128 mg, 5 mol%) and styrene (1.25 g, 12 mmol) were added to the reaction solution.

바이엘을 잘 밀봉한 후 반응용액을 135℃의 온도로 4시간 동안 교반한 다음 유기용매를 감압 건조기로 제거하고 남은 반응 혼합물을 실리카겔 관 크로마토그라피에 의하여 정제하여 2-피리딜메틸-3-페닐 프로파노에이트를 71%의 수율로 얻었다. After sealing the vial well, the reaction solution was stirred at a temperature of 135 ° C. for 4 hours, the organic solvent was removed with a reduced pressure dryer, and the remaining reaction mixture was purified by silica gel column chromatography to obtain 2-pyridylmethyl-3-phenylpropane. Panoate was obtained in a yield of 71%.

1H NMR (CDCl3, 250 MHz) δ 8.58 (d, 1H, J = 4.5 Hz), 7.66 (td, 1H, J = 7.7, 1.7 Hz), 7.31-7.19 (m, 7H), 5.23 (s, 2H), 3.00 (t, 2H, J = 7.5 Hz), 2.76 (t, 2H, J = 7.5 Hz); 13C NMR (CDCl3, 62.5 MHz) δ 173.0, 156.1, 149.9, 140.7, 137.2, 129.0, 128.8, 126.7, 123.3, 122.2, 67.2, 36.2, 31.3; IR (neat) 2943, 2024, 1972, 1941, 1740, 1596, 1448, 1156, 756, 700 cm-1. 1 H NMR (CDCl 3 , 250 MHz) δ 8.58 (d, 1H, J = 4.5 Hz), 7.66 (td, 1H, J = 7.7, 1.7 Hz), 7.31-7.19 (m, 7H), 5.23 (s, 2H), 3.00 (t, 2H, J = 7.5 Hz), 2.76 (t, 2H, J = 7.5 Hz); 13 C NMR (CDCl 3 , 62.5 MHz) δ 173.0, 156.1, 149.9, 140.7, 137.2, 129.0, 128.8, 126.7, 123.3, 122.2, 67.2, 36.2, 31.3; IR (neat) 2943, 2024, 1972, 1941, 1740, 1596, 1448, 1156, 756, 700 cm -1 .

<실시예 5> 2-피리딜메틸-3-(2,4,6-트리메틸페닐) 프로파노에이트 합성Example 5 2-Pyridylmethyl-3- (2,4,6-trimethylphenyl) propanoate synthesis

5 mL의 바이엘에 2-피리딜메틸 포르메이 (548 mg, 4.0 mmol)을 넣고 유기용매로 1,2-디클로에탄(2 mL)을 첨가하여 균일한 용액으로 만든 후 트리스루테니움 도데카카르보닐 화합물(128 mg, 5 mol%)와 2,4,6-트리메틸스티렌(1.75 g, 12 mmol)을 반응용액에 첨가하였다. 2-pyridylmethyl formay (548 mg, 4.0 mmol) was added to 5 mL of Bayer and 1,2-dichloroethane (2 mL) was added as an organic solvent to make a uniform solution. A ribonyl compound (128 mg, 5 mol%) and 2,4,6-trimethylstyrene (1.75 g, 12 mmol) were added to the reaction solution.

바이엘을 잘 밀봉한 후 반응용액을 135℃의 온도로 7시간 동안 교반한 다음 유기용매를 감압 건조기로 제거하고 남은 반응 혼합물을 실리카겔 관 크로마토그라피에 의하여 정제하여 2-피리딜메틸-3-(2,4,6-트리메틸페닐) 프로파노에이트를 95%의 수율로 얻었다. After sealing the vial well, the reaction solution was stirred at a temperature of 135 ° C. for 7 hours, then the organic solvent was removed with a reduced pressure dryer, and the remaining reaction mixture was purified by silica gel column chromatography to obtain 2-pyridylmethyl-3- (2). , 4,6-trimethylphenyl) propanoate was obtained in 95% yield.

1H NMR (CDCl3, 250 MHz) δ 8.60 (d, 1H, J = 4.5 Hz), 7.69 (td, 1H, J = 7.7, 1.7 Hz), 7.32 (d, 1H, J = 7.8 Hz), 7.26-7.21 (m, 1H), 6.84 (s, 2H), 5.27 (s, 2H), 2.99 (m, 2H), 2.56 (m, 2H), 2.29 (s, 6H), 2.25 (s, 3H); 13C NMR (CDCl3, 62.5 MHz) δ 173.3, 156.2, 150.0, 137.2, 136.5, 136.1, 134.3, 129.5, 123.3, 122.2, 67.3, 33.9, 25.1, 21.2, 20.1. 1 H NMR (CDCl 3 , 250 MHz) δ 8.60 (d, 1H, J = 4.5 Hz), 7.69 (td, 1H, J = 7.7, 1.7 Hz), 7.32 (d, 1H, J = 7.8 Hz), 7.26 -7.21 (m, 1H), 6.84 (s, 2H), 5.27 (s, 2H), 2.99 (m, 2H), 2.56 (m, 2H), 2.29 (s, 6H), 2.25 (s, 3H); 13 C NMR (CDCl 3 , 62.5 MHz) δ 173.3, 156.2, 150.0, 137.2, 136.5, 136.1, 134.3, 129.5, 123.3, 122.2, 67.3, 33.9, 25.1, 21.2, 20.1.

<실시예 6> 2-피리딜메틸-3-(2,4,6-트리메틸페닐)프로파노에이트 합성Example 6 Synthesis of 2-pyridylmethyl-3- (2,4,6-trimethylphenyl) propanoate

5 mL의 바이엘에 2-피리딜메틸 포르메이트(548 mg, 4.0 mmol)을 넣고 유기용매로 테트라히드로퓨란(2 mL)을 첨가하여 균일한 용액으로 만든 후 트리스루테니움 도데카카르보닐 화합물(128 mg, 5 mol%)와 2,4,6-트리메틸스티렌(1.75 g, 12 mmol)을 반응용액에 첨가하였다. 2-pyridylmethyl formate (548 mg, 4.0 mmol) was added to 5 mL of Bayer, and tetrahydrofuran (2 mL) was added as an organic solvent to make a uniform solution, followed by trisruthenium dodecacarbonyl compound ( 128 mg, 5 mol%) and 2,4,6-trimethylstyrene (1.75 g, 12 mmol) were added to the reaction solution.

바이엘을 잘 밀봉한 후 반응용액을 135℃의 온도로 5시간 동안 교반한 다음 유기용매를 감압 건조기로 제거하고 남은 반응 혼합물을 실리카겔 관 크로마토그라피에 의하여 정제하여 2-피리딜메틸-3-(2,4,6-트리메틸페닐)프로파노에이트를 69%의 수율로 얻었다. After sealing the vial well, the reaction solution was stirred at a temperature of 135 ° C. for 5 hours, the organic solvent was removed with a reduced pressure dryer, and the remaining reaction mixture was purified by silica gel column chromatography to obtain 2-pyridylmethyl-3- (2). , 4,6-trimethylphenyl) propanoate was obtained in a yield of 69%.

1H NMR (CDCl3, 250 MHz) δ 8.50 (d, 1H, J = 4.5 Hz), 7.70 (td, 1H, J = 7.7, 1.8 Hz), 7.34 (d, 1H, J = 7.3 Hz), 7.23 (m, 1H), 5.23 (s, 2H), 2.44 (t, 2H, J = 7.4 Hz), 1.69 (m, 2H), 0.53 (m, 2H), -0.02 (s, 9H); 13C NMR (CDCl3, 62.5 MHz) δ 173.8, 156.4, 150.0, 137.2, 123.2, 122.2, 67.0, 38.2, 20.2, 16.9, -1.4; IR (neat) 2924, 2029, 1952, 1741, 1577, 1442, 1153 cm-1; HRMS (EI) calcd for C13H21NO2Si 251.1342 (M+), found 251.1342. 1 H NMR (CDCl 3 , 250 MHz) δ 8.50 (d, 1H, J = 4.5 Hz), 7.70 (td, 1H, J = 7.7, 1.8 Hz), 7.34 (d, 1H, J = 7.3 Hz), 7.23 (m, 1H), 5.23 (s, 2H), 2.44 (t, 2H, J = 7.4 Hz), 1.69 (m, 2H), 0.53 (m, 2H), -0.02 (s, 9H); 13 C NMR (CDCl 3 , 62.5 MHz) δ 173.8, 156.4, 150.0, 137.2, 123.2, 122.2, 67.0, 38.2, 20.2, 16.9, -1.4; IR (neat) 2924, 2029, 1952, 1741, 1577, 1442, 1153 cm −1 ; HRMS (EI) calcd for C 13 H 21 NO 2 Si 251.1342 (M + ), found 251.1342.

<실시예 7> 2-피리딜메틸-2,3-디메틸-6-옥소헵타노에이트 합성Example 7 Synthesis of 2-pyridylmethyl-2,3-dimethyl-6-oxoheptanoate

5 mL의 바이엘에 2-피리딜메틸 포르메이트(548 mg, 4.0 mmol)을 넣고 유기용매로 디메틸포름아미드(2 mL)을 첨가하여 균일한 용액으로 만든 후 트리스루테니움 도데카카르보닐 화합물(128 mg, 5 mol%)와 5-메틸-5-헵텐-2-온(1.35 g, 12 mmol)을 반응용액에 첨가하였다. 2-pyridylmethyl formate (548 mg, 4.0 mmol) was added to 5 mL of Bayer, and dimethylformamide (2 mL) was added as an organic solvent to make a uniform solution, followed by trisruthenium dodecacarbonyl compound ( 128 mg, 5 mol%) and 5-methyl-5-hepten-2-one (1.35 g, 12 mmol) were added to the reaction solution.

바이엘을 잘 밀봉한 후 반응용액을 135℃의 온도로 5시간 동안 교반한 다음 유기용매를 감압 건조기로 제거하고 남은 반응 혼합물을 실리카겔 관 크로마토그라피에 의하여 정제하여 2-피리딜메틸-2,3-디메틸-6-옥소헵타노에이트를 65%의 수율로 얻었다. After sealing the vial well, the reaction solution was stirred at a temperature of 135 ° C. for 5 hours, the organic solvent was removed with a reduced pressure dryer, and the remaining reaction mixture was purified by silica gel column chromatography to obtain 2-pyridylmethyl-2,3- Dimethyl-6-oxoheptanoate was obtained in a yield of 65%.

1H NMR (CDCl3, 250 MHz) δ 8.58 (d, 1H, J = 4.8 Hz), 7.70 (td, 1H, J = 7.7, 1.7 Hz), 7.35 (d, 1H, J = 7.8 Hz), 7.23 (m, 1H), 5.23 (s, 2H), 2.50-2.22 (m, 4H), 2.14 (s, 3H), 2.00 (m, 1H), 1.72-1.48 (m, 2H), 0.97 (d, 3H, J = 6.6 Hz); 13C NMR (CDC3, 62.5 MHz) δ 208.9, 172.8, 156.2, 149.8, 137.1, 123.2, 122.2, 67.1, 41.8, 41.6, 30.6, 30.2, 19.9; IR (neat) 2963, 1712, 1596, 1439, 1361, 1154, 915, 732 cm-1. 1 H NMR (CDCl 3 , 250 MHz) δ 8.58 (d, 1H, J = 4.8 Hz), 7.70 (td, 1H, J = 7.7, 1.7 Hz), 7.35 (d, 1H, J = 7.8 Hz), 7.23 (m, 1H), 5.23 (s, 2H), 2.50-2.22 (m, 4H), 2.14 (s, 3H), 2.00 (m, 1H), 1.72-1.48 (m, 2H), 0.97 (d, 3H , J = 6.6 Hz); 13 C NMR (CDC 3 , 62.5 MHz) δ 208.9, 172.8, 156.2, 149.8, 137.1, 123.2, 122.2, 67.1, 41.8, 41.6, 30.6, 30.2, 19.9; IR (neat) 2963, 1712, 1596, 1439, 1361, 1154, 915, 732 cm -1 .

<실시예 8> 2-피리딜메틸-4-옥소펜타노에이트 합성Example 8 Synthesis of 2-pyridylmethyl-4-oxopentanoate

5 mL의 바이엘에 2-피리딜메틸 포르메이트(548 mg, 4.0 mmol)을 넣고 유기용매로 디메틸포름아미드(2 mL)을 첨가하여 균일한 용액으로 만든 후 트리스루테니움 도데카카르보닐 화합물(128 mg, 5 mol%)와 메틸비닐케톤(841 mg, 12 mmol)을 반응용액에 첨가하였다. 2-pyridylmethyl formate (548 mg, 4.0 mmol) was added to 5 mL of Bayer, and dimethylformamide (2 mL) was added as an organic solvent to make a uniform solution, followed by trisruthenium dodecacarbonyl compound ( 128 mg, 5 mol%) and methyl vinyl ketone (841 mg, 12 mmol) were added to the reaction solution.

바이엘을 잘 밀봉한 후 반응용액을 135℃의 온도로 4시간 동안 교반한 다음 유기용매를 감압 건조기로 제거하고 남은 반응 혼합물을 실리카겔 관 크로마토그라피에 의하여 정제하여 2-피리딜메틸-4-옥소펜타노에이트를 68%의 수율로 얻었다. After sealing the vial well, the reaction solution was stirred at a temperature of 135 ° C. for 4 hours, the organic solvent was removed with a vacuum dryer, and the remaining reaction mixture was purified by silica gel column chromatography to obtain 2-pyridylmethyl-4-oxopenta. Noate was obtained with a yield of 68%.

1H NMR (CDCl3, 250 MHz) δ 8.59 (d, 1H, J = 4.7 Hz), 7.72 (td, 1H, J = 7.7, 1.7 Hz), 7.37 (d, 1H, J = 7.8 Hz), 7.24 (m, 1H), 5.25 (s, 2H), 2.84-2.68 (m, 4H), 2.18 (s, 3H); 13C NMR (CDCl3, 62.5 MHz) δ 207.1, 172.9, 156.1, 149.8, 137.3, 123.3, 122.1, 67.3, 38.3, 30.3, 28.3; IR (neat) 2929, 1742, 1741, 1457, 1357, 1157, 999, 735 cm-1. 1 H NMR (CDCl 3 , 250 MHz) δ 8.59 (d, 1H, J = 4.7 Hz), 7.72 (td, 1H, J = 7.7, 1.7 Hz), 7.37 (d, 1H, J = 7.8 Hz), 7.24 (m, 1 H), 5.25 (s, 2 H), 2.84-2.68 (m, 4 H), 2.18 (s, 3 H); 13 C NMR (CDCl 3 , 62.5 MHz) δ 207.1, 172.9, 156.1, 149.8, 137.3, 123.3, 122.1, 67.3, 38.3, 30.3, 28.3; IR (neat) 2929, 1742, 1741, 1457, 1357, 1157, 999, 735 cm -1 .

<실시예 9> 2-피리딜메틸시클로헥산 카르복실레이트 합성Example 9 2-Pyridylmethylcyclohexane Carboxylate Synthesis

5 mL의 바이엘에 2-피리딜메틸 포르메이트(548 mg, 4.0 mmol)을 넣고 유기용매로 디메틸포름아미드(2 mL)을 첨가하여 균일한 용액으로 만든 후 트리스루테니움 도데카카르보닐 화합물(128 mg, 5 mol%)와 시클로헥센(986 mg, 12 mmol)을 반응용액에 첨가하였다. 2-pyridylmethyl formate (548 mg, 4.0 mmol) was added to 5 mL of Bayer, and dimethylformamide (2 mL) was added as an organic solvent to make a uniform solution, followed by trisruthenium dodecacarbonyl compound ( 128 mg, 5 mol%) and cyclohexene (986 mg, 12 mmol) were added to the reaction solution.

바이엘을 잘 밀봉한 후 반응용액을 135℃의 온도로 12시간 동안 교반한 다음 유기용매를 감압 건조기로 제거하고 남은 반응 혼합물을 실리카겔 관 크로마토그라피에 의하여 정제하여 2-피리딜메틸시클로헥산 카르복실레이트를 91%의 수율로 얻었다.After sealing the vial well, the reaction solution was stirred at a temperature of 135 ° C. for 12 hours, the organic solvent was removed with a reduced pressure dryer, and the remaining reaction mixture was purified by silica gel column chromatography to obtain 2-pyridylmethylcyclohexane carboxylate. Was obtained in a yield of 91%.

1H NMR (CDCl3, 250 MHz) δ 8.59 (d, 1H, J = 4.8 Hz), 7.71 (td, 1H, J = 7.7, 1.7 Hz), 7.34 (d, 1H, J = 7.8 Hz), 7.22 (m, 1H), 5.24 (s, 2H), 2.42 (m, 1H), 2.00 (tt, 2H, J = 11.1, 4.0), 1.98-1.25 (m, 8H); 13C NMR (CDCl3, 62.5 MHz) δ 176.1, 156.6, 149.8, 137.2, 123.2, 121.9, 66.9, 43.5, 29.4, 26.1, 25.8; IR (neat) 2936, 2859, 1737, 1595, 1448, 1168, 760 cm-1; HRMS (EI) calcd for C13H17NO2 219.1260 (M+1), found 219.1262. 1 H NMR (CDCl 3 , 250 MHz) δ 8.59 (d, 1H, J = 4.8 Hz), 7.71 (td, 1H, J = 7.7, 1.7 Hz), 7.34 (d, 1H, J = 7.8 Hz), 7.22 (m, 1H), 5.24 (s, 2H), 2.42 (m, 1H), 2.00 (tt, 2H, J = 11.1, 4.0), 1.98-1.25 (m, 8H); 13 C NMR (CDCl 3 , 62.5 MHz) δ 176.1, 156.6, 149.8, 137.2, 123.2, 121.9, 66.9, 43.5, 29.4, 26.1, 25.8; IR (neat) 2936, 2859, 1737, 1595, 1448, 1168, 760 cm −1 ; HRMS (EI) calcd for C 13 H 17 NO 2 219.1260 (M +1 ), found 219.1262.

<실시예 10> 엑소-(2-피리딜메틸)비시클로[2,2,1]헵탄 카르복실레이트 합성Example 10 Synthesis of Exo- (2-pyridylmethyl) bicyclo [2,2,1] heptane carboxylate

5 mL의 바이엘에 2-피리딜메틸 포르메이트(548 mg, 4.0 mmol)을 넣고 유기용매로 디메틸포름아미드(2 mL)을 첨가하여 균일한 용액으로 만든 후 트리스루테니움 도데카카르보닐 화합물(128 mg, 5 mol%)와 놀보닐렌(1.13 g, 12 mmol)을 반응용액에 첨가하였다. 2-pyridylmethyl formate (548 mg, 4.0 mmol) was added to 5 mL of Bayer, and dimethylformamide (2 mL) was added as an organic solvent to make a uniform solution, followed by trisruthenium dodecacarbonyl compound ( 128 mg, 5 mol%) and nobornylene (1.13 g, 12 mmol) were added to the reaction solution.

바이엘을 잘 밀봉한 후 반응용액을 135℃의 온도로 12시간 동안 교반한 다음 유기용매를 감압 건조기로 제거하고 남은 반응 혼합물을 실리카겔 관 크로마토그라피에 의하여 정제하여 엑소-(2-피리딜메틸)비시클로[2,2,1]헵탄 카르복실레이트를 87%의 수율로 얻었다.After sealing the vial well, the reaction solution was stirred at a temperature of 135 ° C. for 12 hours, the organic solvent was removed with a reduced pressure drier, and the remaining reaction mixture was purified by silica gel column chromatography to obtain an exo- (2-pyridylmethyl) ratio. Cyclo [2,2,1] heptane carboxylate was obtained in 87% yield.

1H NMR (CDCl3, 250 MHz) δ 8.58 (d, 1H, J = 4.6 Hz), 7.68 (t, 1H, J = 7.7 Hz), 7.31 (d, 1H, J = 7.8 Hz), 7.2 (m, 1H), 5.22 (s, 2H), 2.56 (s, 1H), 2.43 (dd, 1H, J = 9.0, 5.3 Hz), 2.31 (s, 1H), 1.86 (m, 1H), 1.52 (m, 4H), 1.23 (m, 3H); 13C NMR (CDCl3, 62.5 MHz) δ 176.0, 156.6, 149.8, 137.1, 123.1, 121.9, 67.0, 46.8, 41.4, 36.9, 36.4, 34.5, 29.8, 29.0; IR (neat) 2959, 2875, 1735, 1171, 759 cm-1; HRMS (EI) calcd for C14H15NO3 229.1072 (M+ ), found 229.1069. 1 H NMR (CDCl 3 , 250 MHz) δ 8.58 (d, 1H, J = 4.6 Hz), 7.68 (t, 1H, J = 7.7 Hz), 7.31 (d, 1H, J = 7.8 Hz), 7.2 (m , 1H), 5.22 (s, 2H), 2.56 (s, 1H), 2.43 (dd, 1H, J = 9.0, 5.3 Hz), 2.31 (s, 1H), 1.86 (m, 1H), 1.52 (m, 4H), 1.23 (m, 3H); 13 C NMR (CDCl 3 , 62.5 MHz) δ 176.0, 156.6, 149.8, 137.1, 123.1, 121.9, 67.0, 46.8, 41.4, 36.9, 36.4, 34.5, 29.8, 29.0; IR (neat) 2959, 2875, 1735, 1171, 759 cm −1 ; HRMS (EI) calcd for C 14 H 15 NO 3 229.1072 (M + ), found 229.1069.

<실시예 11> (2-피리딜메틸)테트라히드로피란-2-카르복실레이트 합성Example 11 Synthesis of (2-pyridylmethyl) tetrahydropyran-2-carboxylate

5 mL의 바이엘용기에 2-피리딜메틸 포르메이트(548 mg, 4.0 mmol)을 넣고 유기용매로 테트라히드로퓨란(2 mL)을 첨가하여 균일한 용액으로 만든 후 트리스루테니움 도데카카르보닐 화합물(128 mg, 5 mol%)와 3,4-디히드로-2H-피란(1.01 g, 12 mmol)을 반응용액에 첨가하였다. 2-pyridylmethyl formate (548 mg, 4.0 mmol) was added to a 5 mL Bayer container, and tetrahydrofuran (2 mL) was added as an organic solvent to make a uniform solution, followed by trisruthenium dodecacarbonyl compound. (128 mg, 5 mol%) and 3,4-dihydro-2H-pyran (1.01 g, 12 mmol) were added to the reaction solution.

바이엘을 잘 밀봉한 후 반응용액을 135℃의 온도로 12시간 동안 교반한 다음 유기용매를 감압 건조기로 제거하고 남은 반응 혼합물을 실리카겔 관 크로마토그라피에 의하여 정제하여 (2-피리딜메틸)테트라히드로피란-2-카르복실레이트를 76%의 수율로 얻었다.After sealing the vial well, the reaction solution was stirred at a temperature of 135 ° C. for 12 hours, the organic solvent was removed with a reduced pressure dryer, and the remaining reaction mixture was purified by silica gel column chromatography (2-pyridylmethyl) tetrahydropyran -2-carboxylate was obtained in 76% yield.

1H NMR (CDC3, 250 MHz) δ 8.51 (d, 1H, J = 4.4 Hz), 7.62 (t, 1H, J = 7.6 Hz), 7.43 (d, 1H, J = 7.8 Hz), 7.14 (m, 1H), 4.84 (ABq, 1H, J = 13.4 Hz), 4.74 (s, 1H), 4.61 (ABq, 1H, J = 13.4 Hz), 3.87 (m, 1H), 3.53 (m, 1H), 1.79-1.49 (m, 6H); 13C NMR (CDCl3, 62.5 MHz) δ 149.5, 136.9, 122.6, 121.8, 98.9, 70.3, 62.6, 30.9, 25.8, 19.7; IR (neat) 2942, 2865, 1737, 1598, 1436, 1127, 1027, 965, 756 cm-1. 1 H NMR (CDC 3 , 250 MHz) δ 8.51 (d, 1H, J = 4.4 Hz), 7.62 (t, 1H, J = 7.6 Hz), 7.43 (d, 1H, J = 7.8 Hz), 7.14 (m , 1H), 4.84 (ABq, 1H, J = 13.4 Hz), 4.74 (s, 1H), 4.61 (ABq, 1H, J = 13.4 Hz), 3.87 (m, 1H), 3.53 (m, 1H), 1.79 -1.49 (m, 6 H); 13 C NMR (CDCl 3 , 62.5 MHz) δ 149.5, 136.9, 122.6, 121.8, 98.9, 70.3, 62.6, 30.9, 25.8, 19.7; IR (neat) 2942, 2865, 1737, 1598, 1436, 1127, 1027, 965, 756 cm -1 .

<실시예 12> 2-피리딜메틸-2-뷰틸옥시 프로파노에이트 합성Example 12 Synthesis of 2-pyridylmethyl-2-butyloxy propanoate

5 mL의 바이엘에 2-피리딜메틸 포르메이트(548 mg, 4.0 mmol)을 넣고 유기용매로 1,2-디클로에탄(2 mL)을 첨가하여 균일한 용액으로 만든 후 트리스루테니움 도데카카르보닐 화합물(128 mg, 5 mol%)와 뷰틸비닐에테르(1.20 g, 12 mmol)을 반응용액에 첨가하였다. 2-pyridylmethyl formate (548 mg, 4.0 mmol) was added to 5 mL of Bayer, and 1,2-dichloroethane (2 mL) was added as an organic solvent to make a uniform solution. A ribonyl compound (128 mg, 5 mol%) and butyl vinyl ether (1.20 g, 12 mmol) were added to the reaction solution.

바이엘을 잘 밀봉한 후 반응용액을 135℃의 온도로 12시간 동안 교반한 다음 유기용매를 감압 건조기로 제거하고 남은 반응 혼합물을 실리카겔 관 크로마토그라피에 의하여 정제하여 2-피리딜메틸-2-뷰틸옥시 프로파노에이트를 64%의 수율로 얻었다.After sealing the vial well, the reaction solution was stirred at a temperature of 135 ° C. for 12 hours, the organic solvent was removed using a vacuum dryer, and the remaining reaction mixture was purified by silica gel column chromatography to obtain 2-pyridylmethyl-2-butyloxy. Propanoate was obtained in a yield of 64%.

1H NMR (CDCl3, 250 MHz) δ 8.55 (d, 1H, J = 4.7 Hz), 7.69 (td, 1H, J = 7.7, 1.7 Hz), 7.45 (d, 1H, J = 7.8 Hz), 7.18 (m, 1H), 4.88 (q, 1H, J = 5.3 Hz), 4.77 (ABq, 1H, J = 13.4 Hz), 4.66 (ABq, 1H, J = 13.4 Hz), 3.66-3.46 (m, 2H), 1.57 (m, 2H), 1.40 (m, 5H), 0.91 (t, 3H, J = 7.3 Hz); 13C NMR (CDCl3, 62.5 MHz) δ 159.2, 149.4, 137.0, 122.6, 121.7, 100.3, 68.2, 66.0, 32.3, 20.2, 19.8, 14.3; IR (neat) 2935, 2874, 1740, 1594, 1471, 1382, 1096, 916, 759 cm-1; HRMS (EI) calcd for C13H19NO3 237.1366 (M+), found 237.1364. 1 H NMR (CDCl 3 , 250 MHz) δ 8.55 (d, 1H, J = 4.7 Hz), 7.69 (td, 1H, J = 7.7, 1.7 Hz), 7.45 (d, 1H, J = 7.8 Hz), 7.18 (m, 1H), 4.88 (q, 1H, J = 5.3 Hz), 4.77 (ABq, 1H, J = 13.4 Hz), 4.66 (ABq, 1H, J = 13.4 Hz), 3.66-3.46 (m, 2H) , 1.57 (m, 2H), 1.40 (m, 5H), 0.91 (t, 3H, J = 7.3 Hz); 13 C NMR (CDCl 3 , 62.5 MHz) δ 159.2, 149.4, 137.0, 122.6, 121.7, 100.3, 68.2, 66.0, 32.3, 20.2, 19.8, 14.3; IR (neat) 2935, 2874, 1740, 1594, 1471, 1382, 1096, 916, 759 cm −1 ; HRMS (EI) calcd for C 13 H 19 NO 3 237.1366 (M + ), found 237.1364.

본 발명에 의하면 일산화탄소를 사용하지 않아도 되는 온화한 반응조건 하에서 올레핀으로부터 고수율과 고선택성으로 올레핀에 비하여 탄소수가 하나 더 늘어난 에스테르 화합물을 제조할 수 있다.According to the present invention, under mild reaction conditions in which carbon monoxide is not used, an ester compound having one more carbon number than the olefin can be prepared from the olefin in high yield and high selectivity.

Claims (9)

에스테르의 제조에 있어서,In the preparation of esters, 하기 화학식(1)의 피리딜알킬 포르메이트를 루테니움 착화합물 촉매 존재하에서 올레핀과 반응시켜 하기 화학식(2)의 에스테르 화합물을 얻는 것을 특징으로 하는 올레핀으로부터 에스테르의 제조방법.A pyridylalkyl formate of formula (1) is reacted with an olefin in the presence of a ruthenium complex catalyst to obtain an ester compound of formula (2). 상기 화학식(1) 및 화학식(2)에서 R은 알킬, 시클로알킬, 알케닐, 시클로알케닐, 알키닐, 아릴 또는 질소, 산소 혹은 황원자를 1개 이상 함유하는 헤테로아릴을 나타내며 n은 0∼3의 정수를 나타낸다. In Formulas (1) and (2), R represents alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, aryl or heteroaryl containing one or more nitrogen, oxygen or sulfur atoms, n is 0 to 3 Represents an integer. 제 1항에 있어서,The method of claim 1, 알킬, 알케닐 또는 알키닐은 탄소원자 1 에서 18개로 구성됨을 특징으로 하는 에스테르의 제조방법.Alkyl, alkenyl or alkynyl is a process for preparing an ester, characterized in that it consists of 1 to 18 carbon atoms. 제 1항에 있어서, The method of claim 1, 시클로알킬은 탄소원자 3에서 8개로 구성됨을 특징으로 하는 에스테르의 제조방법Cycloalkyl is a process for preparing an ester, characterized in that it consists of 3 to 8 carbon atoms 제 1항에 있어서,The method of claim 1, 시클로알케닐은 탄소원자 3 에서 7개로 구성되며, 환상 이중결합을 1개 이상 포함함을 특징으로 하는 에스테르의 제조방법.Cycloalkenyl is composed of 7 to 3 carbon atoms, the method for producing an ester, characterized in that it comprises at least one cyclic double bond. 제 1항에 있어서,The method of claim 1, 아릴은 페닐 또는 나프틸임을 특징으로 하는 에스테르의 제조방법.Aryl is phenyl or naphthyl. 제 1항에 있어서,The method of claim 1, 헤테로아릴은 피리딜, 퓨라닐 또는 티에닐임을 특징으로 하는 에스테르의 제조방법.Heteroaryl is pyridyl, furanyl or thienyl. 제 1항에 있어서, 루테니움 착화합물은 The compound of claim 1, wherein the ruthenium complex is 하기 화학식(3)인 것을 특징으로 하는 에스테르의 제조방법Method for producing an ester, characterized in that the formula (3) Rup(CO)q(X)r 화학식(3)Ru p (CO) q (X) r Formula (3) 상기 화학식(3)에서 X는 클로로 또는 브로모이며, p는 1∼4, q는 4∼12, r은 0∼2 사이의 수를 나타낸다. In the formula (3), X is chloro or bromo, p is 1-4, q is 4-12, r represents a number between 0-2. 제 1항에 있어서, 루테니움 착화합물은 The compound of claim 1, wherein the ruthenium complex is 상기 화학식(1)의 화합물을 기준으로 1∼5몰% 사용하는 것을 특징으로 하는 에스테르의 제조방법.A method for producing an ester, characterized in that 1 to 5 mol% based on the compound of formula (1). 제 1항에 있어서, The method of claim 1, 반응은 100∼160℃에서 0.5∼24시간 동안 실시하는 것을 특징으로 하는 에스테르의 제조방법.The reaction is carried out at 100 to 160 ° C for 0.5 to 24 hours.
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Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
Journal of Molecular Catalysis, 1989 *
Keim,Wilhelm; Becker, Johannes; J Mol Catal; 1989; Vol.54; No.1; p95-101 *
Kondo, Teruyuki; J Mol Catal 1989; Vol.50; No.1; p31-38 *
Nahmed, El Mostafa et al; J Mol Catal, Vol 59; No.3; L15-L19 *
Ueda, W; Yokoyama, T; Morikawa, Y et al; J Mol Catal 1988; Vol.44; No.2; p197-200 *

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