WO2000055135A1 - P rocede de production d'un derive pyridine par reaction d'azametallacyclo pentadiene avec de l'alkyne - Google Patents
P rocede de production d'un derive pyridine par reaction d'azametallacyclo pentadiene avec de l'alkyne Download PDFInfo
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- WO2000055135A1 WO2000055135A1 PCT/JP2000/000075 JP0000075W WO0055135A1 WO 2000055135 A1 WO2000055135 A1 WO 2000055135A1 JP 0000075 W JP0000075 W JP 0000075W WO 0055135 A1 WO0055135 A1 WO 0055135A1
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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
- C07D213/06—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 containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
- C07D213/16—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 containing only hydrogen and carbon atoms in addition to the ring nitrogen atom containing only one pyridine ring
-
- 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
- C07D213/06—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 containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
- C07D213/08—Preparation by ring-closure
-
- 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
- C07D213/06—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 containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
- C07D213/08—Preparation by ring-closure
- C07D213/09—Preparation by ring-closure involving the use of ammonia, amines, amine salts, or nitriles
- C07D213/12—Preparation by ring-closure involving the use of ammonia, amines, amine salts, or nitriles from unsaturated compounds
Definitions
- the present invention is directed to the use of azametallic pentagens, especially pre-periodic transition metals, in the presence of stoichiometric transition metal complexes, preferably Ni (II) complexes. Based on the reaction between pentagens and alkynes, the position can be selected from two different alkynes and two trinoles.
- stoichiometric transition metal complexes preferably Ni (II) complexes.
- Pyridines are important as intermediates and final chemicals in many chemical products such as pharmaceuticals, pesticides, cross-linking agents, etc. Using easy-to-access raw materials, using simple processes (fewer processes), and conducting the reaction selectively and functionally (radio-positionally). There has been a desire to develop a method.
- the process is very similar to the process for producing relayanes by alkyne trimerization, and uses the same catalyst, for example, CpCo. (cod), CpCo (CO) 2 etc. are adopted in both processes. It is.
- the problem to be solved by the present invention is to use a readily available raw material to produce pyridines by a simple process (fewer processes) and to recover pyridines.
- An object of the present invention is to develop and provide a production method in which the obtained reaction proceeds with good functional group selectivity and regioselectivity.
- the present inventors have proposed a method for producing pyridines by regioselectively reacting the above-mentioned known intermediate with a second alkylene. I thought it could not be solved.
- reaction for producing pyridines by reacting azazircona cyclopentagen with alkynes can be assumed to be the following reaction formula 1. .
- M represents an early transition metal.
- L is a pentenyl group, an indenyl group, a fluorenyl group, an azulenyl group, a hydrocarbon group, or an amide.
- R 3, R 4, and R 5 are each a substituted or unsubstituted alkyl group, an alkenyl group, an aromatic group, or a silyl group having 1 to 20 carbon atoms. Group, acrekoxy group, and ester group. )
- the inventors of the present invention conducted a reaction between triethylazazazirconacyclopentadiene and 3—hexene in a stoichiometric amount of CuCl 1. The reaction to be performed in the presence of was examined.
- a method of producing an array in the presence of the above-mentioned stoichiometric amount of CuC1 has a remarkable power, such as a positional selectivity estimated from a method of producing an array. There was no match for control.
- Ni C 12 (PPh 3) 2 was used instead of Cu C 1 at 50 ° C, the pentaethyl pyridin was used. (2a) (in the case of R ethyl group) was formed in a yield of 7% (Reaction Scheme 2).
- asymmetrically substituted pyridines can be prepared by force coupling of two different types of phenols and trinolequines.
- an object of the present invention is to provide a method for obtaining pyridines having good functional group selectivity and regioselectivity based on the above presumption. Disclosure of the invention
- the gist of the present invention is that a transition between an azametaracyclopentagen represented by the general formula (1) and an alkyne represented by the general formula (2) is performed.
- M represents a preceding transition metal, particularly preferably Zr, Ti, and Hf.
- L represents a cyclopentene group, an indeninole group, or a phenol group.
- n When the number is 2 or more, a combination of different ligands may be used.
- R l, R 2 and R 3 each represent a substituted or unsubstituted alkyl group, alkyl group, or aromatic group having 1 to 20 carbon atoms.
- Shiri Nore represents an alkyl group, an alkoxy group, or an ester group.
- R 4 and R 5 have the same meaning as R 1, R 2 and R 3, respectively, and are each a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms. , An alkenyl group, an aromatic group, a silyl group, an alkoxy group, and an ester group.
- the pyridines are characterized in that an Ni (II) complex represented by the general formula NiXmLn is used as the transition metal complex. How to build.
- NiXmLn L represents a neutral ligand
- n an integer of 1 to 4.
- X represents an anionic ligand
- m represents 1 to 4 (If n and m represent integers of 2 or more, different combinations of ligands may be used.)
- the present inventors have found that the reaction of azazinoleconic cyclopentadidin with phenols in the presence of a stoichiometric amount of Ni (II) complex is particularly desirable. Thus, the above-mentioned problem has been solved.
- the first step consists in the selective formation of the ginolekonashik mouth penten4 by the reaction of zirconacyclopentan3 with phenolic
- the reaction of zircona cyclopentene 4 with nitrolinole gives rear-a-zirconic cyclopentenes 1.
- the reaction is as follows (reaction formula 3).
- a combination of an alkyne having a different substituent and a nitrile has a different aza-zirconic pen having a different substituent. Tangerines can be generated.
- a particularly preferred embodiment of the present invention is a substitution which is different depending on the reaction between the azazirconium-opening pentagens having the above substituents and the phenols. This is to obtain pyridines having a group.
- R 1 to R 3 include methyl, ethyl, propynole, isopropropyl, butynole, isobutynole, t-butyl, pentinole, neopentinole, and hexagon. Cinole, Occhinore, Noninore, Desinore, Cyclopentinole, Cyclohexinole, Cyclonecinole, etc., quinole group, binore, arinore, etc.
- Aryloxy groups such as phenolic, phenoxy, and naphthoxy, methyl cane boxate, ethyl carboxylate, propanolate Boxile, Isopropynole Canolate Boxyrate, Butyl Caneol Key sheet les over preparative, Lee Seo Buchinore force Honoré volume key sheet rate, t - Buchinoreka Rubo key sheet rate, full et two Honoré force Honoré volume key fractionated scan te le groups such rate is listed et is Ru.
- R 1 to R 3 Particularly preferred groups for R 1 to R 3 are methinore, echinole, n-butinole, t-butinole, hexinole, feninole, trimethylsilyl, methinole.
- Norebox rate, etch force Norebox rate, t — Vitaminole box rate, f ⁇ nole nox box rate is preferred, ethyl, n — Butinore, t — Butinole, hexyl, trimethyltinyl, and methyl caneboxylate are even more preferred.
- suitable binding groups include, specifically, (a) a methylene group, an ethylene group, an isopropylene group, and a diphenyl group.
- Phenylene group such as thiylene group, (mouth) silylene group, dimethylinosilylene group, disilylene group, tetramethylethyldisilylene, etc.
- it is an alkylene group or a silylene group.
- the transition metal in the transition metal complex is not particularly limited, but is preferably selected.
- Table 1 summarizes the reaction raw materials, generated pyridines, and yields.
- This method can also be applied to azazirconine dendine which produces a substituted isoquinoline derivative 2h (Example 6) after the reaction.
- the present invention relates to two different alkynes (including alkynes used in the process of synthesizing azametaracyclopentadiene). ) And nitrile as raw materials, and it is possible to synthesize (substantially) regio-selectively (regi 0 se Iecti V e) substituted pyridines. The effect is brought about.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Pyridine Compounds (AREA)
Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US09/675,000 US6365744B1 (en) | 1999-03-12 | 2000-01-11 | Process for producing pyridine derivative through reaction of azametallacyclopentadiene with alkyne |
EP00900170A EP1078920B1 (en) | 1999-03-12 | 2000-01-11 | Process for producing pyridine derivative through reaction of azametal lacyclo pentadiene with alkyne |
DE60012275T DE60012275T2 (de) | 1999-03-12 | 2000-01-11 | Verfahren zur herstellung von pyridinderivaten durch reaktion von azametall-acyclopentadien mit alkin |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP11/65992 | 1999-03-12 | ||
JP06599299A JP4180723B2 (ja) | 1999-03-12 | 1999-03-12 | アザメタラシクロペンタジエン類とアルキン類との反応によるピリジン類の製造方法 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2000055135A1 true WO2000055135A1 (fr) | 2000-09-21 |
Family
ID=13303027
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2000/000075 WO2000055135A1 (fr) | 1999-03-12 | 2000-01-11 | P rocede de production d'un derive pyridine par reaction d'azametallacyclo pentadiene avec de l'alkyne |
Country Status (5)
Country | Link |
---|---|
US (1) | US6365744B1 (ja) |
EP (1) | EP1078920B1 (ja) |
JP (1) | JP4180723B2 (ja) |
DE (1) | DE60012275T2 (ja) |
WO (1) | WO2000055135A1 (ja) |
Families Citing this family (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2003082191A2 (en) | 2002-03-28 | 2003-10-09 | Merck & Co., Inc. | Substituted 2,3-diphenyl pyridines |
CA2751892A1 (en) | 2009-01-15 | 2010-07-22 | Rutgers, The State University Of New Jersey | Benzo [c] phenanthridines as antimicrobial agents |
WO2010127307A1 (en) | 2009-04-30 | 2010-11-04 | Rutgers, The State University Of New Jersey | Antimicrobial agents |
CA2810162A1 (en) | 2010-06-09 | 2011-12-15 | Rutgers, The State University Of New Jersey | Antimicrobial agents |
US9102617B2 (en) | 2010-06-25 | 2015-08-11 | Rutgers, The State University Of New Jersey | Antimicrobial agents |
US9822108B2 (en) | 2012-01-13 | 2017-11-21 | Rutgers, The State University Of New Jersey | Antimicrobial agents |
WO2013142712A1 (en) | 2012-03-21 | 2013-09-26 | Rutgers, The State University Of New Jersey | Antimicrobial agents |
US9458150B2 (en) | 2013-11-08 | 2016-10-04 | Rutgers, The State University Of New Jersey | Antimicrobial agents |
US10513528B2 (en) | 2016-02-25 | 2019-12-24 | Taxis Pharmaceuticals, Inc. | Synthetic processes and intermediates |
CN110891566B (zh) | 2017-03-30 | 2023-12-19 | 塔克西斯医药股份有限公司 | 合成方法和合成中间体 |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4477673A (en) * | 1982-01-27 | 1984-10-16 | Ciba-Geigy Corporation | Process for the preparation of substituted divinylpyridines and novel substituted divinylpyridines |
US4588815A (en) * | 1981-05-02 | 1986-05-13 | Studiengesellschaft Kohle Mbh | Method for manufacturing pyridine and pyridine derivatives from alkynes and cyano compounds in the presence of complex cobalt or rhodium compounds with ligands containing boron |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0110177B1 (en) * | 1982-11-06 | 1989-03-22 | Denki Kagaku Kogyo Kabushiki Kaisha | Substituted cyclopentadienyl cobalt complexes and synthesis of pyridine homologues by means of the complexes |
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1999
- 1999-03-12 JP JP06599299A patent/JP4180723B2/ja not_active Expired - Fee Related
-
2000
- 2000-01-11 WO PCT/JP2000/000075 patent/WO2000055135A1/ja active IP Right Grant
- 2000-01-11 US US09/675,000 patent/US6365744B1/en not_active Expired - Lifetime
- 2000-01-11 EP EP00900170A patent/EP1078920B1/en not_active Expired - Lifetime
- 2000-01-11 DE DE60012275T patent/DE60012275T2/de not_active Expired - Lifetime
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4588815A (en) * | 1981-05-02 | 1986-05-13 | Studiengesellschaft Kohle Mbh | Method for manufacturing pyridine and pyridine derivatives from alkynes and cyano compounds in the presence of complex cobalt or rhodium compounds with ligands containing boron |
US4477673A (en) * | 1982-01-27 | 1984-10-16 | Ciba-Geigy Corporation | Process for the preparation of substituted divinylpyridines and novel substituted divinylpyridines |
Non-Patent Citations (1)
Title |
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See also references of EP1078920A4 * |
Also Published As
Publication number | Publication date |
---|---|
DE60012275D1 (de) | 2004-08-26 |
EP1078920A4 (en) | 2001-05-30 |
EP1078920B1 (en) | 2004-07-21 |
DE60012275T2 (de) | 2005-07-28 |
EP1078920A1 (en) | 2001-02-28 |
US6365744B1 (en) | 2002-04-02 |
JP4180723B2 (ja) | 2008-11-12 |
JP2000256321A (ja) | 2000-09-19 |
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