KR101761200B1 - Preparation method of Pyridoisoquinolinone derivatives - Google Patents
Preparation method of Pyridoisoquinolinone derivatives Download PDFInfo
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- GZCYJBVZPNELTH-UHFFFAOYSA-N CCOC(C1=C(C=CC(C)=C2)C2=C(C=CC=C2)N2C1=O)=O Chemical compound CCOC(C1=C(C=CC(C)=C2)C2=C(C=CC=C2)N2C1=O)=O GZCYJBVZPNELTH-UHFFFAOYSA-N 0.000 description 1
- YEGRPBCFFXNOJU-UHFFFAOYSA-N CCOC(C1=C(C=CC=C2)C2=C(C=CC(C(C)=O)=C2)N2C1=O)=O Chemical compound CCOC(C1=C(C=CC=C2)C2=C(C=CC(C(C)=O)=C2)N2C1=O)=O YEGRPBCFFXNOJU-UHFFFAOYSA-N 0.000 description 1
- YSFVIZZWWFHCCD-UHFFFAOYSA-N CCOC(C1=C(C=CC=C2)C2=C(c2ccccc2C=C2)N2C1=O)=O Chemical compound CCOC(C1=C(C=CC=C2)C2=C(c2ccccc2C=C2)N2C1=O)=O YSFVIZZWWFHCCD-UHFFFAOYSA-N 0.000 description 1
- VWWQKRJWYPQXGC-UHFFFAOYSA-N CCOC(C1=C(C=CC=C2C)C2=C2N=CC=CN2C1=O)=O Chemical compound CCOC(C1=C(C=CC=C2C)C2=C2N=CC=CN2C1=O)=O VWWQKRJWYPQXGC-UHFFFAOYSA-N 0.000 description 1
- ZBRYXMBYYGUALK-ORHIOLHHSA-N NC1C=C(CC[C@]([C@@](CC2)(C(CC3)C2=O)I)([C@@]32I)I)C2=CC1N Chemical compound NC1C=C(CC[C@]([C@@](CC2)(C(CC3)C2=O)I)([C@@]32I)I)C2=CC1N ZBRYXMBYYGUALK-ORHIOLHHSA-N 0.000 description 1
- FNLPNPGTWOATKA-UHFFFAOYSA-N NC1C=C2OCOC2=CC1N Chemical compound NC1C=C2OCOC2=CC1N FNLPNPGTWOATKA-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
- C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
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- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D491/00—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00
- C07D491/12—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00 in which the condensed system contains three hetero rings
- C07D491/14—Ortho-condensed systems
- C07D491/153—Ortho-condensed systems the condensed system containing two rings with oxygen as ring hetero atom and one ring with nitrogen as ring hetero atom
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Abstract
The present invention relates to a process for producing a pyrido isoquinolinone derivative represented by the following general formula (1).
[Chemical Formula 1]
In Formula 1, A ring, B ring, R 1 , R 2 , R 3 , a and b are each as defined in the description of the invention.
Description
The present invention relates to a process for the preparation of pyrido isoquinolinone derivatives.
Carbonylation of metal carbene is very important in organic chemistry. Among them, the carbonylation reaction using a palladium catalyst is a method widely used for synthesizing a carbonyl functional material. In addition, manganese, iron, platinum, rhodium, and cobalt have been reported, but most reactions requiring high pressure and temperature .
Recently conjugated polyhedral cyclic compounds have attracted much attention due to the variety of electron, photoelectron and magnetic properties. In addition, the conjugation poly ring compound containing a new ring has a change in physical properties, so development of a new synthetic method is very important.
In the present invention, pyrido isoquinolinone derivatives are synthesized by carbonylation, carbonylation, and intramolecular cyclization in the presence of a pyridinyldiazoacetate derivative as a starting material in the presence of a cobalt catalyst.
Thus, in order to develop an easy and effective synthesis method that is easy to use and easy to use, the present invention utilizes intramolecular carbonylation from pyridinyldiazoacetate derivatives derived from 2-phenylpyridine of various substrates, It is expected that it will be usefully applied as a synthesis method more effective for synthesizing such electron, photoelectron and magnetic characteristic or fluorescent compound.
Accordingly, an object of the present invention is to provide a process for producing a pyrido isoquinolinone derivative through an intramolecular cyclization reaction using a cobalt catalyst.
The present invention relates to a process for producing a pyrido isoquinolinone derivative represented by the following general formula (1), wherein a pyridinyldiazoacetate derivative represented by the following general formula (2) is subjected to carbonylation and intramolecular cyclization reaction with a cobalt catalyst in the presence of carbon monoxide, 1 < / RTI > pyrido isoquinolinone derivatives.
[Chemical Formula 1]
(2)
[In the above formulas (1) and (2)
Ring A and ring B are each independently (C6-20) aromatic ring or (C3-C20) heteroaromatic ring;
R < 1 > is (C1-C20) alkyl;
R 2 and R 3 are each independently selected from the group consisting of (C 1 -C 20) alkyl, (C 1 -C 20) alkoxy, halo (C 1 -C 20) alkyl, (C 1 -C 20) alkoxycarbonyl, (C 1 -C 20) alkyl, cyano or (C 1 -C 20) alkylcarbonyl, or R 2 and R 3 may each be connected to adjacent substituents to form a fused ring or multiple fused rings -CH 2 - of the fused ring or multiple fused rings may be substituted with -C (= O) - to form a ketone group within the fused ring or multiple fused rings, wherein the fused or multiple fused rings may be substituted with (C 1 -C 20 (C1-C20) alkyl, (C1-C20) alkoxy, halo (C1-C20) alkyl, (C6-20) aryl and (C6-20) aryl
a and b each independently represents an integer of 0 to 2.]
Hereinafter, the present invention will be described in detail.
Here, unless otherwise defined in the technical terms and the scientific terms used, those having ordinary skill in the art to which the present invention belongs have the same meaning as commonly understood by those skilled in the art. Repeated descriptions of the same technical constitution and operation as those of the conventional art will be omitted.
The present invention relates to a process for producing a pyrido isoquinolinone derivative represented by the following general formula (1), wherein a pyridinyldiazoacetate derivative represented by the following general formula (2) is subjected to carbonylation and intramolecular cyclization in the presence of a cobalt catalyst and carbon monoxide gas, Wherein the pyrido isoquinolinone derivative is represented by the following formula (1).
[Chemical Formula 1]
(2)
[In the above formulas (1) and (2)
Ring A and ring B are each independently (C6-20) aromatic ring or (C3-C20) heteroaromatic ring;
R < 1 > is (C1-C20) alkyl;
R 2 and R 3 are each independently selected from the group consisting of (C 1 -C 20) alkyl, (C 1 -C 20) alkoxy, halo (C 1 -C 20) alkyl, (C 1 -C 20) alkoxycarbonyl, (C 1 -C 20) alkyl, cyano or (C 1 -C 20) alkylcarbonyl, or R 2 and R 3 may each be connected to adjacent substituents to form a fused ring or multiple fused rings -CH 2 - of the fused ring or multiple fused rings may be substituted with -C (= O) - to form a ketone group within the fused ring or multiple fused rings, wherein the fused or multiple fused rings may be substituted with (C 1 -C 20 (C1-C20) alkyl, (C1-C20) alkoxy, halo (C1-C20) alkyl, (C6-20) aryl and (C6-20) aryl
a and b each independently represents an integer of 0 to 2.]
The pyridinyldiazoacetate derivative of Formula 2 is prepared by reacting a pyridinylaryl acetate derivative of Formula 3 with a tosyl azide (TsN 3 ).
(3)
Wherein A ring, B ring, R 1 , R 2 , R 3 , a and b are the same as defined in the above formula (1).
&Quot; Alkyl " and " alkoxy ", as used in the present invention, include both linear and branched forms.
&Quot; Aryl " in the present invention means an organic radical derived from an aromatic hydrocarbon by one hydrogen elimination and is a single or fused ring containing 4 to 7, preferably 5 or 6 ring atoms, And includes a form in which a plurality of aryls are connected by a single bond. Specific examples of the aryl group include aromatic groups such as phenyl, naphthyl, biphenyl, indenyl, fluorenyl, phenanthrenyl, anthracenyl, triphenylenyl, pyrenyl, .
An " aromatic ring " as defined in the present invention is an aromatic system consisting of a hydrocarbon comprising one or more rings, which may be a single or fused ring system containing in each ring suitably 4 to 7, preferably 5 or 6 ring atoms . Specific examples thereof include benzene, naphthalene, and anthracene.
The "heteroaromatic ring" described in the present invention is an aromatic monocyclic or multicyclic ring system having 3 to 20 carbon atoms and having at least one heteroatom selected from O, S or N. Specific examples include pyrazine, isothiazole, oxazole, pyrazole, pyrrole, pyridazine, thienopyrimidine, furan, quinazolinyl, pyridine, thiophene, quinoline and isoquinoline.
In Formula 1 and Formula 2 according to an embodiment of the present invention, A ring is benzene, naphthalene, thiophene or a ring selected from the following structures;
R 'is (C1-C10) alkyl; The B ring may be pyridine, quinoline, isoquinoline or pyrimidine.
In the above formulas (1) and (2) according to an embodiment of the present invention, R 1 is (C 1 -C 10) alkyl; R 2 and R 3 are each independently selected from the group consisting of (C 1 -C 10) alkyl, (C 1 -C 10) alkoxy, halo (C 1 -C 10) alkyl, (C 1 -C 10) alkoxycarbonyl, C6-20) aryl (C1-C20) alkyl, cyano or (C1-C10) alkylcarbonyl; a and b each independently may be an integer of 0 to 2;
In the above formulas (1) and (2) according to an embodiment of the present invention, R 1 is (C 1 -C 7) alkyl; R 2 and R 3 are each independently selected from the group consisting of (C 1 -C 7) alkyl, (C 1 -C 7) alkoxy, halo (C 1 -C 7) alkyl, (C 1 -C 7) alkoxycarbonyl, C6-12) aryl (C1-C7) alkyl, cyano or (C1-C7) alkylcarbonyl; a and b may each independently be an integer of 0 or 1.
More specifically, R 1 is methyl, ethyl, propyl or butyl, more particularly in Formulas 1 and 2 according to one embodiment of the present invention; R 2 and R 3 are each independently selected from methyl, ethyl, propyl, butyl, methoxy, ethoxy, propoxy, butoxy, chloro, fluoro, bromo, cyano, trifluoromethyl, methoxycarbonyl, Ethoxycarbonyl, methylcarbonyl, ethylcarbonyl, phenyl, biphenyl, naphthyl or benzyl; a and b may each independently be an integer of 0 or 1.
The pyrido isoquinolinone derivative of Formula 1 according to an embodiment of the present invention may be selected from the following structures, but is not limited thereto.
The process for preparing the pyrido isoquinolinone derivative of the formula (1) according to the present invention is a process for producing a pyrido isoquinolinone derivative, which is a product of high yield and purity in a simple process and in a mild condition in the presence of a cobalt catalyst and carbon monoxide, It is an effective method.
The cobalt (Co) catalyst according to an embodiment of the present invention may include Co (OAc) 2 .4H 2 O [OAc = acetate], Co (acac) 2 [acac = acetylacetonate], CoCl 2 .6H 2 O, CoBr 2 xH 2 O, CoSO 4 · 7H 2 O, Co (NO 3) 2 · 6H 2 O, Co (PPh 3) 2 Cl 2, may be one or more which is Co 2 (CO) 8 selected from, more preferably Co 2 (CO) < / RTI > 8 .
The amount of the cobalt catalyst according to an embodiment of the present invention may be 0.01 to 0.30 mol, preferably 0.02 to 0.15 mol, based on 1 mol of the pyridinyldiazoacetate derivative represented by the formula (2). If the cobalt catalyst is used in the above range, the pyrido isoquinolinone derivative of the formula (1) can be produced at a high yield, and if it is out of the above range, the yield and economical efficiency may be lowered.
In an embodiment of the present invention, the reaction may be carried out in an organic solvent, and it is not necessary to limit the organic solvent as long as it can dissolve the reactant. The organic solvent according to an exemplary embodiment of the present invention may be selected from the group consisting of tetrahydrofuran, 1,4-dioxane, acetonitrile, toluene, And toluene can be used more preferably.
According to an embodiment of the present invention, the reaction may be carried out at room temperature. The reaction time may vary depending on the reactants, the kind of the solvent, and the amount of the solvent, and the starting material, pyridinyl After confirming that the diazoacetate derivative is completely consumed, the reaction is completed. When the reaction is completed, the solvent can be distilled off under reduced pressure, and the desired product can be separated and purified through a conventional method such as column chromatography.
The pyrido isoquinolinone derivatives according to the present invention are conjugated polyhedral ring compounds and have a variety of electron, photoelectron and magnetic properties. The process for preparing the pyrido isoquinolinone derivative according to the present invention can be carried out by intramolecular carbonylation reaction using a cobalt catalyst and carbon monoxide, and a pyrido isoquinolinone derivative can do.
Hereinafter, the structure of the present invention will be described in more detail with reference to examples. However, the following examples are provided to aid understanding of the present invention, and the scope of the present invention is not limited thereto.
Example 1-ethyl-6-oxo -6 H - pyrido [2,1, a] isoquinolin-7-carboxylate (ethyl 6-oxo-6 H -pyrido [2,1- a] isoquinoline-7 -carboxylate
A reaction vessel ethyl 2-diazo-2- (2- (pyridin-2-yl) phenyl) acetate (53.5 mg, 0.2 mmol), Co 2 (CO) 8 (1.4 mg, 0.004 mmol) and toluene (1.75 mL) were added, and carbon monoxide bubbling was performed for 1 minute, followed by stirring at room temperature for 5 hours. The solvent was removed and the residue was purified by column chromatography (acetone: MC = 1: 4) to obtain the objective compound, ethyl-6-oxo- 6H -pyrido [2,1 a ] isoquinoline-7-carboxylate 95%, 50.8 mg).
1 H NMR (400 MHz, CDCl 3) δ 9.98 (dd, J = 7.0 Hz , J = 0.7 Hz, 1H), 8.73 (d, J = 8.8 Hz, 1H), 8.32 (d, J = 8.5 Hz, 1H), 8.13-8.08 (m, 1H), 7.66 (td, J = 10.5 Hz , J = 1.3 Hz, 1H), 7.62-7.58 (m, 1H), 7.28-7.24 (m, 1H), 4.56 (q, J = 7.1 Hz, 2H), 1.49 (t , ≪ / RTI > J = 7.1 Hz, 3H)
Example 2 Ethyl-11-methyl-6-oxo--6 H - pyrido [2,1, a] isoquinolin-7-carboxylate (ethyl 11-methyl-6- oxo-6 H -pyrido [2 , L- a ] isoquinoline-7-carboxylate
Diazo-2- (3-methyl-2- (pyridin-2-yl) phenyl) acetate (prepared in Example 1) was used instead of ethyl 2-diazo-2- except that (56.3 mg, 0.2 mmol) and is conducted by reacting the same manner as that of example 1, the desired compound, ethyl-11-methyl-6-oxo--6 H-pyrido [2,1, a] isoquinolin- 7-carboxylate (87%, 47.0 mg).
1 H NMR (400 MHz, CDCl 3) δ 9.98 (d, J = 6.8 Hz , 1H), 8.77 (d, J = 8.6 Hz, 1H), 8.03-8.00 (m, 1H), 7.74 (d, J = 8.2 Hz, 1H), 7.61 (t, J = 6.5 Hz, 1H), 7.43 (t, J = 7.7 Hz, 1H), 7.08 (d, J = 6.5 Hz, 1H), 4.55 (q, J = 7.1 Hz, 2H) 1.48 (t, J = 7.1 Hz, 3 H)
Example 3 Ethyl-10-methyl-6-oxo--6 H - pyrido [2,1, a] isoquinolin-7-carboxylate (ethyl 10-methyl-6- oxo-6 H -pyrido [2 , L- a ] isoquinoline-7-carboxylate
Diazo-2- (4-methyl-2- (pyridin-2-yl) phenyl) acetate (prepared in Example 1) was used instead of ethyl 2-diazo-2- 10-methyl-6-oxo- 6H -pyrido [2,1, a ] isoquinoline-2-carboxylic acid ethyl ester was prepared by the same procedure as in Example 1, except that the title compound (56.3 mg, 0.2 mmol) 7-carboxylate (80%, 45.0 mg).
1 H NMR (400 MHz, CDCl 3) δ 7.89 (d, J = 8.8 Hz, 1H), 7.58 (td, J ), 9.89 (d, J = 7.0 Hz, 1H), 8.64 (d, J = 8.8 Hz, 1H), 8.05-8.01 = 10.4 Hz, J = 1.1 Hz , 1H), 7.40 (dd, J = 8.8 Hz, J = 1.4 Hz, 1H), 4.55 (q, J = 7.1 Hz, 2H), 2.46 (s, 3H), 1.48 ( t, J = 7.1 Hz, 3H)
Example 4 Ethyl 9-methyl-6-oxo--6 H - pyrido [2,1, a] isoquinolin-7-carboxylate (ethyl 9-methyl-6- oxo-6 H -pyrido [2 , L- a ] isoquinoline-7-carboxylate
Diazo-2- (5-methyl-2- (pyridin-2-yl) phenyl) acetate (prepared in Example 1) was used instead of ethyl 2-diazo-2- Methyl-6-oxo- 6H -pyrido [2,1, a ] isoquinoline-2-carboxylic acid methyl ester (56.3 mg, 0.2 mmol) was reacted in the same manner as in Example 1, 7-carboxylate (91%, 51.2 mg).
1 H NMR (400 MHz, CDCl 3) δ 9.84 (d, J = 6.5 Hz , 1H), 8.58 (d, J = 8.6 Hz, 1H), 8.13 (d, J = 8.6 Hz, 1H), 8.03-7.98 (m, 1H), 7.74 (s, 1H ), 7.57-7.53 (m, 1H) , 7.04-7.02 (m, 1H), 4.56 (q, J = 7.1 Hz, 2H), 2.45 (s, 3H), 1.50 (t, J = 7.1 Hz, 3H)
Example 5 Ethyl 9-methoxy-6-oxo--6 H - pyrido [2,1, a] isoquinolin-7-carboxylate (ethyl 9-methoxy-6- oxo-6 H -pyrido [ 2,1- a ] isoquinoline-7-carboxylate
Diazo-2- (5-methoxy-2- (pyridin-2-yl) phenyl) acetate (prepared in Example 1) was used instead of ethyl 2-diazo-2- by reaction in the same manner as in example 1, except that the (59.5 mg, 0.2 mmol) the desired compound, ethyl 9-methoxy-6-oxo--6 H - pyrido [2,1, a] isoquinoline -7-carboxylate (81%, 48.0 mg).
1 H NMR (400 MHz, CDCl 3) δ 9.82 (d, J = 7.0 Hz , 1H), 8.50 (d, J = 8.8 Hz, 1H), 8.19 (d, J = 9.2 Hz, 1H), 7.97 (t, J = 7.8 Hz, 1H), 7.50 ( (t, J = 7.0 Hz, 2H), 6.86 (dd, J = 9.3 Hz, J = 1.3 Hz, 1H), 4.54 (q, J = 7.1 Hz, 2H) J = 7.1 Hz, 3H)
Example 6 Ethyl 6-oxo -6 H - [1,3] dioxo [4,5, - g] pyrido [2,1, a] isoquinolin-7-carboxylate (ethyl 6-oxo -6H- [1,3] dioxolo [4,5-g] pyrido [2,1-a] isoquinoline-7-carboxylate
Ethyl 2-diazo-2- (6- (pyridin-2-yl) benzo [d] [1, 3] dioxol-5-yl) acetate (62.3 mg, by the reaction in the same manner as in example 1, except that the 0.2 mmol) -6-oxo-6-ethyl target compound H - [1,3] dioxo [4,5, -g ] pyrido [2,1, a ] isoquinoline-7-carboxylate (80%, 50.0 mg).
1 H NMR (400 MHz, CDCl 3) δ 9.90 (dq, J = 6.7 Hz , J = 0.7 Hz, 1H), 8.59 (d, J = 8.8 Hz, 1H), 8.06-8.00 (m, 2H), 7.60 (td, J = 7.0 Hz, J = 1.3 Hz, 1H), 6.95 (d , J 9.0 Hz, 1H), 6.16 (s, 2H), 4.49 (q, J = 7.1 Hz, 2H), 1.43 (t, J = 7.1 Hz, 3H)
[Example 7] -6-oxo-6-ethyl-9-H-pyrido [2,1, a] isoquinolin-7-carboxylate (ethyl 9-fluoro-6- oxo-6 H -pyrido [ 2,1- a ] isoquinoline-7-carboxylate
Diazo-2- (5-fluoro-2- (pyridin-2-yl) phenyl) acetate (prepared in Example 1) was used instead of ethyl 2-diazo-2- 6-oxo- 6H -pyrido [2,1, a ] isoquinoline (57.13 mg, 0.2 mmol) was obtained in the same manner as in Example 1, -7-carboxylate (88%, 50.6 mg).
1 H NMR (400 MHz, CDCl 3) δ 9.83 (d, J = 6.9 Hz , 1H), 8.56 (d, J = 8.8 Hz, 1H), 8.24 (dd, J = 9.3 Hz, J = 5.7 Hz, 1H), 8.12-8.08 (m, 1H), 7.71 (dd, J = 11.9 Hz , J = 2.4 Hz, 1H), 7.61 (td, J = 10.4 Hz, J = 1.0 Hz, 1H), 6.94-6.90 (m, 1H), 4.54 (q, J = 7.1 Hz, 2H), 1.49 (t, J = 7.1 Hz, 3H)
Example 8 10-chloro-6-oxo-ethyl -6 H - pyrido [2,1, a] isoquinolin-7-carboxylate (ethyl 10-chloro-6- oxo-6 H -pyrido [2 , L- a ] isoquinoline-7-carboxylate
(4-chloro-2- (pyridin-2-yl) phenyl) -2-diazoacetate was obtained in the same manner as in Example 1, except that ethyl ethyl 2- 10-chloro-6-oxo- 6H -pyrido [2,1, a ] isoquinoline-2-carboxylic acid ethyl ester (60.3 mg, 0.2 mmol) was reacted in the same manner as in Example 1, Carboxylate (91%, 55.0 mg).
1 H NMR (400 MHz, CDCl 3) δ 9.95 (d, J = 6.8 Hz , 1H), 8.64 (d, J = 8.7 Hz, 1H), 8.25 (d, J = 2.0 Hz, 1H), 8.16-8.12 (m, 1H), 8.07 (d, J = 9.2 Hz, 1H), 7.71 (t, J = 6.9 Hz, 1H), 7.51 (dd, J = 9.2 Hz, J = 2.0 Hz, 1H), 4.54 (q, J = 7.1 Hz, 2H), 1.48 ( t, J = 7.1 Hz, 3H)
Example 9 Ethyl 9-chloro-6-oxo -6 H - pyrido [2,1, a] isoquinolin-7-carboxylate (ethyl 9-chloro-6- oxo-6 H -pyrido [2 , L- a ] isoquinoline-7-carboxylate
(5-chloro-2- (pyridin-2-yl) phenyl) -2-diazoacetate (prepared in Example 1) was used instead of ethyl 2-diazo-2- 56.3 mg, by the reaction in the same manner as in example 1, except that the 0.2 mmol) of the desired compound ethyl 9-chloro-6- oxo -6 H - pyrido [2,1, a] isoquinoline -7 -Carboxylate (87%, 47.0 mg).
1 H NMR (400 MHz, CDCl 3) δ 9.82 (dd, J = 7.0 Hz , J = 0.8 Hz, 1H), 8.57 (d, J = 8.7 Hz, 1H), 8.13-8.09 (m, 2H), 7.98 (d, J = 2.0 Hz, 1H), 7.64 (td, J = 10.5 Hz , J = 1.3 Hz, 1H), 7.07 (dd, J = 9.0 Hz, J = 2.1 Hz, 1H), 4.54 (q, J = 7.1 Hz, 2H), 1.50 (t, J = 7.1 Hz, 3H)
[Example 10] Preparation of ethyl 6-oxo-9- (trifluoromethyl) -6 H -pyrido [2,1 a ] isoquinoline- -6 H -pyrido [2,1- a] isoquinoline -7-carboxylate) Preparation of
Diazo-2- (2- (pyridin-2-yl) -5- (trifluoromethyl) phenyl) acetate was used in the place of ethyl 2-diazo-2- ) acetate (67.1 mg, example 1, methyl and ethyl-6-oxo-9- (trifluoromethyl was reacted in the same manner except that the desired compound 0.2 mmol)) -6 H - pyrido [2, L, a ] isoquinoline-7-carboxylate (70%, 47.0 mg).
1 H NMR (400 MHz, CDCl 3) δ 9.91 (d, J = 6.8 Hz , 1H), 8.72 (d, J = 8.6 Hz, 1H), 8.36-8.33 (m, 1H), 8.21 (t, J = 7.4 Hz, 1H), 7.75 (t, J = 6.9 Hz, 1H), 7.33-7.31 (m, 1H), 4.56 (q, J = 7.1 Hz, 2H), 1.50 (t, J = 7.1 Hz,
Example 11 Ethyl 9-cyano-6-oxo--6 H - pyrido [2,1, a] isoquinolin-7-carboxylate (ethyl 9-cyano-6- oxo-6 H -pyrido [ 2,1- a ] isoquinoline-7-carboxylate
(5-cyano-2- (pyridin-2-yl) phenyl) -2-diazoacetate (prepared in Example 1) instead of ethyl 2-diazo-2- 6-oxo- 6H -pyrido [2,1, a ] isoquinoline-2-carboxylic acid ethyl ester was obtained in the same manner as in Example 1, 7-carboxylate (72%, 42.0 mg).
1 H NMR (400 MHz, CDCl 3) δ 10.02 (d, J = 6.8 Hz , 1H), 8.77 (d, J = 8.6 Hz, 1H), 8.53 (s, 1H), 8.37 (d, J = 8.8 Hz, 1H), 8.31-8.26 (m, 1H ), 7.85 (t, J = 6.7 Hz, 1H), 7.34 (dd, J = 8.7 Hz, J = 1.2 Hz, 1H), 4.56 (q, J = 7.1 Hz, 2H), 1.50 (t, J = 7.1 Hz, 3H)
Example 12 Ethyl 9-acetyl-6-oxo--6 H - pyrido [2,1, a] isoquinolin-7-carboxylate (ethyl 9-acetyl-6- oxo-6 H -pyrido [2 , L- a ] isoquinoline-7-carboxylate
(5-acetyl-2- (pyridin-2-yl) phenyl) -2-diazoacetate (prepared in Example 1) was used instead of ethyl 2-diazo-2- 6-oxo- 6H -pyrido [2,1, a ] isoquinoline-7 (1 H) -Carboxylate (84%, 52.0 mg).
1 H NMR (400 MHz, CDCl 3) δ 10.04 (d, J = 6.9 Hz , 1H), 8.82-8.79 (m, 2H), 8.39 (d, J = 8.9 Hz, 1H), 8.23-8.19 (m, 1H), 7.80-7.77 (m, 2H) , 4.59 (q, J = 7.1 Hz, 2H), 2.73 (s, 3H), 1.52 (t, J = 7.1 Hz, 3H)
Example 13 diethyl 6-oxo -6 H - pyrido [2,1, a] isoquinolin--7,9- dimethyl carboxylate (diethyl 6-oxo-6 H -pyrido [2,1- a ] isoquinoline-7,9-dicarboxylate)
A reaction vessel ethyl 3- (1-diazo-2 -ethoxy-2-oxoethyl) -4- (pyridin-2-yl) benzoate (67.9 mg, 0.2 mmol), Co 2 (CO) 8 (10.3 mg, 0.03 mmol) and toluene (1.75 mL) were added to the solution, and carbon monoxide bubbling was performed for 1 minute, followed by stirring at room temperature for 5 hours. The solvent was removed and the residue was purified by column chromatography (acetone: MC = 1: 4) to obtain the objective diethyl-6-oxo- 6H -pyrido [2,1 a ] isoquinoline- Dicarboxylate (94%, 64.0 mg) was obtained.
1 H NMR (400 MHz, CDCl 3) δ 9.89 (d, J = 6.7 Hz , 1H), 8.72 (d, J = 8.7 Hz, 1H), 8.64 (d, J = 1.2 Hz, 1H), 8.28 (d, J = 8.9 Hz, 1H), 8.18- 8.14 (m, 1H), 7.73-7.68 (m, 2H), 4.58 (q, J = 7.1 Hz, 2H), 4.44 (q, J = 7.1 Hz, 2H), 1.52 (t, J = 7.1 Hz, 3H ), 1.45 (t, J = 7.1 Hz, 3 H)
Example 14 Ethyl 6-oxo-9-phenyl -6 H - pyrido [2,1, a] isoquinolin-7-carboxylate (ethyl 6-oxo-9- phenyl-6 H -pyrido [2 , L- a ] isoquinoline-7-carboxylate
Ethyl 2-diazo-2- (4- (pyridin-2-yl) - [1,1'- biphenyl] -3-yl) acetate ( 68.7 mg, and by a reaction in the same manner as in example 1 except for using 0.2 mmol) of the desired compound ethyl-6-oxo-9-phenyl -6 H - pyrido [2 , L, a ] isoquinoline-7-carboxylate (85%, 58.5 mg).
1 H NMR (400 MHz, CDCl 3) δ 9.90 (d, J = 6.2 Hz , 1H), 8.67 (d, J = 8.7 Hz, 1H), 8.32 (d, J = 8.8 Hz, 1H), 8.25 (d, J = 1.7 Hz, 1H), 8.08- 8.04 (m, 1H), 7.71 (d, J = 7.0 Hz, 2H), 7.57 (td, J = 10.4 Hz, J = 1.1 Hz, 1H), 7.51-7.40 (m, 4H), 4.58 (q, J = 7.1 Hz, 2H), 1.51 (t, J = 7.1 Hz, 3H)
Example 15 Ethyl 6-oxo -6 H - benzo [h] pyrido [2,1, a] isoquinolin-7-carboxylate (ethyl 6-oxo-6 H -benzo [h] pyrido [2 , L- a ] isoquinoline-7-carboxylate
A reaction vessel ethyl 2-diazo-2- (1- (pyridin-2-yl) naphthalen-2-yl) acetate (63.5 mg, 0.2 mmol), Co 2 (CO) 8 (3.4 mg, 0.01 mmol) and toluene (1.75 mL) were added, and the mixture was bubbled with carbon monoxide for 1 minute, followed by stirring at room temperature for 5 hours. The solvent was removed and the residue was purified by column chromatography (acetone: MC = 1: 4) to obtain the objective compound, ethyl-6-oxo- 6H -benzo [ h ] pyrido [2,1, a ] isoquinoline- -Carboxylate (45%, 29.0 mg).
1 H NMR (400 MHz, CDCl 3) δ 9.80 (dd, J = 6.8 Hz , J = 2.8 Hz, 1H), 8.90 (dd, J = 8.7 Hz, J = 5.4 Hz, 1H), 8.42 (dd, J = 8.2 Hz, J = 4.9 Hz, 1H) , 7.90-7.77 (m, 4H), 7.67-7.57 (m, 1H), 7.52-7.46 (m, 1H), 4.57 (q, J = 7.1 Hz, 2H), 1.49 (t, J = 7.1 Hz, 3H )
Example 16 Ethyl 6-oxo -6 H - benzo [g] pyrido [2,1, a] isoquinolin-7-carboxylate (ethyl 6-oxo-6 H -benzo [g] pyrido [2 , L- a ] isoquinoline-7-carboxylate
Diazo-2- (3- (pyridin-2-yl) acetate) was prepared in the same manner as in Example 15, except that ethyl 2-diazo-2- (1- (pyridin- 2- 6-oxo- 6H -benzo [ g ] pyrido [2, 2-yl] acetate (63.5 mg, 0.2 mmol) 1, a ] isoquinoline-7-carboxylate (76%, 48.4 mg).
1 H NMR (400 MHz, CDCl 3) δ 9.76 (d, J = 6.7 Hz , 1H), 8.67 (d, J = 8.5 Hz, 1H), 8.57 (s, 1H), 8.35 (s, 1H), 8.14-8.10 (m, 1H), 7.72 (d , J = 8.4 Hz, 1H) , 7.64 (d, J = 8.4 Hz, 1H), 7.55 (t, J = 6.9 Hz, 1H), 7.38 (t, J = 7.2 Hz, 1H), 7.25 (t, J = 7.4 Hz, 1H), 4.62 (q, J = 7.1 Hz, 2H), 1.55 (t, J = 7.1 Hz,
Example 17 ethyl-1-methyl-6-oxo--6 H - pyrido [2,1, a] isoquinolin-7-carboxylate (ethyl 1-methyl-6- oxo-6 H -pyrido [2 , L- a ] isoquinoline-7-carboxylate
Ethyl 2-diazo-2- (2- (3-methylpyridin-2-yl) phenyl) acetate (56.3 mg, by the reaction in the same manner as in example 1, except that the 0.2 mmol) of the desired compound ethyl-1-methyl-6-oxo--6 H - pyrido [2,1, a] isoquinolin-7 Carboxylate (80%, 45.0 mg).
1 H NMR (400 MHz, CDCl 3) δ 9.98 (dd, J = 6.8 Hz , J = 0.7 Hz, 1H), 8.38 (d, J = 8.6 Hz, 1H), 8.05 (d, J = 3.1 Hz, 1H), 7.98 (d, J = 3.6 Hz, 1H), 7.59-7.54 (m, 2H ), 7.20-7.16 (m, 1H), 4.54 (q, J = 7.1 Hz, 2H), 3.07 (s, 3H), 1.48 (t, J = 7.1 Hz, 3H )
[Example 18] Ethyl 3-methoxy-6-oxo--6 H - pyrido [2,1, a] isoquinolin-7-carboxylate (ethyl 3-methoxy-6- oxo-6 H -pyrido [ 2,1- a ] isoquinoline-7-carboxylate
Ethyl 2-diazo-2- (2- (5-methoxypyridin-2-yl) phenyl) acetate (56.3 mg, 0.2 mmol), the title compound, ethyl-3-methoxy-6-oxo- 6H -pyrido [2,1, a ] isoquinoline-7 -Carboxylate (88%, 52.0 mg).
1 H NMR (400 MHz, CDCl 3) δ 9.47 (d, J = 2.6 Hz , 1H), 8.55 (d, J = 9.5 Hz, 1H), 8.19 (d, J = 8.5 Hz, 1H), 8.00 (d, J = 8.6 Hz, 1H), 7.74 ( dd, J = 9.5 Hz, J = 2.7 Hz, 1H), 7.55-7.51 (m, 1H), 7.23-7.19 (m, 1H), 4.56 (q, J = 7.1 Hz, 2H), 4.02 (s, 3H ), 1.50 (t, J = 7.1 Hz, 3 H)
Example 19 Ethyl-3-fluoro-6-oxo -6 H - pyrido [2,1, a] isoquinolin-7-carboxylate (ethyl 3-fluoro-6- oxo-6 H -pyrido [ 2,1- a ] isoquinoline-7-carboxylate
Ethyl 2-diazo-2- (2- (5-fluoropyridin-2-yl) phenyl) acetate (57.1 g) was used instead of ethyl 2-diazo-2- mg, 0.2 mmol), the target compound, ethyl 3-fluoro-6-oxo- 6H -pyrido [2,1, a ] isoquinoline-7 -Carboxylate (82%, 47.0 mg).
1 H NMR (400 MHz, CDCl 3) δ 9.72-9.70 (m, 1H), 8.65 (dd, J = 9.6 Hz, J = 5.0 Hz, 1H), 8.17 (d, J = 8.6 Hz, 1H), 7.91-7.87 (m, 2H), 7.54-7.50 (m, 1H), 7.23-7.20 ( m, 1H), 4.54 (q, J = 7.1 Hz, 2H), 1.48 (t, J = 7.1 Hz, 3H)
[Example 20] Ethyl 3-acetylamino-6-oxo--6 H - pyrido [2,1, a] isoquinolin-7-carboxylate (ethyl 3-acetyl-6- oxo-6 H -pyrido [2 , L- a ] isoquinoline-7-carboxylate
Ethyl 2- (5-acetylpyridin-2-yl) phenyl) -2- (2-pyridyl) diazoacetate by the reaction in the same manner as in example 15, except that the (61.8 mg, 0.2 mmol) the desired compound, ethyl 3-acetylamino-6-oxo--6 H - pyrido [2,1, a] isoquinoline -7-carboxylate (92%, 57.0 mg).
1 H NMR (400 MHz, CDCl 3) δ 10.42 (d, J = 1.7 Hz , 1H), 8.69 (d, J = 9.2 Hz, 1H), 8.50 (dd, J = 9.2 Hz, J = 1.9 Hz, 1H), 8.28 (d, J = 8.6 Hz, 1H), 8.00 (d, J = 8.7 Hz, 1H) 7.61-7.57 (m, 1H), 7.27-7.20 (m, 1H), 4.56 (q, J = 7.1 Hz, 2H), 2.79 (s, 3H) , 1.50 (t, J = 7.1 Hz, 3 H)
Example 21 Ethyl 6-oxo -6 H - iso 1,2,3,4 [1,2, a] isoquinolin-5-carboxylate (ethyl 6-oxo-6 H -isoquinolino [1,2- a] isoquinoline- 5-carboxylate
Ethyl 2-diazo-2- (2- (isoquinolin-1-yl) phenyl) acetate (63.5 mg, except for using 0.2 mmol) in example 1 and reacted by the same way the desired compound, ethyl 6-oxo--6 H - iso 1,2,3,4 [1,2, a] isoquinolin-5-carboxylate (45% , 28.7 mg).
1 H NMR (400 MHz, CDCl 3) δ 9.57 (d, J = 7.4 Hz , 1H), 8.81 (d, J = 8.4 Hz, 1H), 8.44 (d, J = 8.7 Hz, 1H), 8.12 (d, J = 4.8 Hz, 1H), 8.00 ( d, J = 7.8 Hz, 1H ), 7.91 (t, J = 7.5 Hz, 1H), 7.82-7.78 (m, 1H), 7.70 (d, J = 7.5 Hz, 1H), 7.61-7.57 (m, 1H ), 7.24-7.20 (m, 1H) , 4.56 (q, J = 7.1 Hz, 2H), 1.49 (t, J = 7.1 Hz, 3H)
Example 22 Ethyl 5-oxo -5 H - no [2,3, a] quinolinyl Jean-4-carboxylate (ethyl 5-oxo-5 H -thieno to Im [2,3- a] quinolizine -4-carboxylate
Diazo-2- (2- (pyridin-2-yl) benzoate was obtained in the same manner as in Example 13, except that ethyl 2- diazo-2- thiophen-3-yl) acetate ( 54.7 mg, 0.2 mmol) and the example 13 by the reaction in the same manner the desired compound ethyl 5-oxo -5 H except that - in the furnace Im [2,3, a ] Quinolizine-4-carboxylate (54%, 30.0 mg).
1 H NMR (400 MHz, CDCl 3) δ 9.63 (d, J = 7.2 Hz , 1H), 8.07 (d, J = 5.5 Hz, 1H), 7.89-7.82 (m, 2H), 7.73 (d, J = 5.5 Hz, 1H), 7.38-7.34 (m J = 7.1 Hz, 2H), 1.48 (t, J = 7.1 Hz, 3H)
[Example 23] Ethyl-11-methyl-6-oxo--6 H - pyrimido [2,1, a] isoquinolin-7-carboxylate (ethyl 11-methyl-6- oxo-6 H -pyrimido [2 , L- a ] isoquinoline-7-carboxylate
Diazo-2- (3-methyl-2- (pyrimidin-2-yl) phenyl) acetate (prepared in Example 1) was used instead of ethyl 2-diazo-2- (56.5 mg, 0.2 mmol) for example 1, was reacted in the same manner as in the desired compound, ethyl-11-methyl-6-oxo--6 H except that - pyrimido [2,1, a] isoquinolin- 7-carboxylate (87%, 47.0 mg).
1 H NMR (400 MHz, CDCl 3) δ 10.09 (dd, J = 7.0 Hz , J = 2.2 Hz, 1H), 9.16 (dd, J = 3.9 Hz, J = 2.2 Hz, 1H), 7.74 (d, J = 8.6 Hz, 1H), 7.62 (dd, J = 7.0 Hz, J = 3.9 , 1H), 7.54-7.50 (m, 1H), 7.13 (d, J = 7.0 Hz, 1H), 4.56 (q, J = 7.1 Hz, 2H), 3.01 (s, 3H ), 1.48 (t, J = 7.1 Hz, 3 H)
[Example 24] (3a R, 3b S , 14b R, 16a R) - ethyl-methyl -16a- -1,12- dioxo -1,2,3,3a, 3b, 4,5,12,14b, (3a R , 3b S , 14b R < / RTI >< RTI ID = 0.0 > , 16a R ) -ethyl 16a-methyl-1,12-dioxo-1,2,3,3a, 3b, 4,5,12,14b,15,16,16a-dodecahydrocyclopenta [5,6] naphtho [ 2- g ] pyrido [2,1- a ] isoquinoline-13-carboxylate
Example 15 ethyl 2-diazo-2- (1- (pyridin-2-yl) naphthalen-2-yl) ethyl 2-diazo-2 in place of acetate - ((8 S, 9 R , 13 R, 14 R ) -13-methyl-17-oxo -3- (pyridin-2-yl) -7,8,9,11,12,13,14,15,16,17-decahydro-6 H -cyclopenta [a] phenanthren -2-yl) acetate (88.7 mg , 3a R ( which by the reaction in the same manner as in example 15, except that the 0.2 mmol) the desired compound, 3b S, 14b R, 16a R) - ethyl-methyl -16a- -1,12-dioxo-1,2,3,3a, 3b, 4,5,12,14b,15,16,16a- dodecahydrocyclopenta [5,6] naphtho [1,2, g ] Pyrido [2,1- a ] isoquinoline-13-carboxylate (82%, 75.0 mg).
1 H NMR (400 MHz, CDCl 3) δ 9.90 (d, J = 7.0 Hz , 1H), 8.63 (d, J = 8.7 Hz, 1H), 8.05-8.00 (m, 3H), 7.58 (t, J = 6.9 Hz, 1H), 4.56 (q, J = 7.1 Hz, 2H), 3.12-2.97 (m, 2H), 2.57-2.50 (m, 2H), 2.41-2.35 (m, 1H), 2.22-2.01 (m, 4H), 1.76-1.48 ), 0.93 (s, 3H)
[Example 25] Ethyl 6-oxo -6 H - pyrido [2,1, a] isoquinolin-7-carboxylate (ethyl 6-oxo-6 H -pyrido [2,1- a] isoquinoline-7 -carboxylate
TsN 3 (0.4 mmol) and DBU (0.4 mmol) were added to the reaction vessel with ethyl 2- (2- (pyridin-2-yl) phenyl) acetate (48.2 mg, 0.2 mmol) and tetrahydrofuran (2.00 mL) And the mixture was stirred at room temperature for 12 hours. Thereafter, the reaction mixture was transferred to a new reaction vessel through silica gel filtration, and then Co 2 (CO) 8 (34.2 mg, 0.1 mmol) and tetrahydrofuran (1.00 mL) were added. The mixture was stirred for 1 hour at room temperature and stirred for 6 hours. The solvent was removed and the residue was purified by column chromatography (acetone: MC = 1: 4) to obtain the objective compound, ethyl-6-oxo- 6H -pyrido [2,1 a ] isoquinoline-7-carboxylate 51%, 29.3 mg).
1 H NMR (400 MHz, CDCl 3) δ 9.98 (dd, J = 7.0 Hz , J = 0.7 Hz, 1H), 8.73 (d, J = 8.8 Hz, 1H), 8.32 (d, J = 8.5 Hz, 1H), 8.13-8.08 (m, 1H), 7.66 (td, J = 10.5 Hz , J = 1.3 Hz, 1H), 7.62-7.58 (m, 1H), 7.28-7.24 (m, 1H), 4.56 (q, J = 7.1 Hz, 2H), 1.49 (t , ≪ / RTI > J = 7.1 Hz, 3H)
Claims (8)
[Chemical Formula 1]
(2)
[In the above formulas (1) and (2)
Ring A and ring B are each independently (C6-20) aromatic ring or (C3-C20) heteroaromatic ring;
R < 1 > is (C1-C20) alkyl;
R 2 and R 3 are each independently selected from the group consisting of (C 1 -C 20) alkyl, (C 1 -C 20) alkoxy, halo (C 1 -C 20) alkyl, (C 1 -C 20) alkoxycarbonyl, (C 1 -C 20) alkyl, cyano or (C 1 -C 20) alkylcarbonyl, or R 2 and R 3 may each be connected to adjacent substituents to form a fused ring or multiple fused rings -CH 2 - of the fused ring or multiple fused rings may be substituted with -C (= O) - to form a ketone group within the fused ring or multiple fused rings, wherein the fused or multiple fused rings may be substituted with (C 1 -C 20 (C1-C20) alkyl, (C1-C20) alkoxy, halo (C1-C20) alkyl, (C6-20) aryl and (C6-20) aryl
a and b each independently represents an integer of 0 to 2.]
Wherein the cobalt catalyst is used in a range of 0.01 to 0.30 mol based on 1 mol of the pyridinyldiazoacetate derivative of the formula (2).
Wherein the reaction is carried out in one or more organic solvents selected from tetrahydrofuran, dioxane, acetonitrile and toluene.
The ring A is a benzene, naphthalene, thiophene or a ring selected from the following structures;
R 'is (C1-C10) alkyl;
And the ring B is pyridine, quinoline, isoquinoline or pyrimidine.
R < 1 > is methyl, ethyl, propyl or butyl; R 2 and R 3 are each independently selected from methyl, ethyl, propyl, butyl, methoxy, ethoxy, propoxy, butoxy, chloro, fluoro, bromo, cyano, trifluoromethyl, methoxycarbonyl, Ethoxycarbonyl, methylcarbonyl, ethylcarbonyl, phenyl, biphenyl, naphthyl or benzyl; and a and b each independently represent an integer of 0 or 1.
Lt; RTI ID = 0.0 > 1, < / RTI >
Wherein the pyridinyldiazoacetate derivative of Formula 2 is prepared by reacting a pyridinylaryl acetate derivative of Formula 3 with a tosyl azide (TsN 3 ).
(3)
Wherein A ring, B ring, R 1 , R 2 , R 3 , a and b are the same as defined in claim 1.
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