Process for the production of pyridine derivatives

Details Process for the production of pyridine derivatives Process for the production of pyridine derivatives

2002-05-29

2003-01-21

Morris, Patricia L. (Department: 1625)

Organic compounds -- part of the class 532-570 series

Organic compounds

Heterocyclic carbon compounds containing a hetero ring...

C546S167000, C546S257000

Reexamination Certificate

active

06509469

ABSTRACT:

TECHNICAL FIELD
The present invention relates to a process capable of producing, at a low cost in a high yield, high-purity pyridine derivatives serving as an important intermediate for the production of pharmaceuticals, agrichemicals, catalyst ligands, silver halide photosensitive materials, liquid crystals and electrophotography, and organic photosensitive materials or dyes used in the field of organic electroluminescence.
BACKGROUND ART
A variety of production processes of substituted pyridines have been reported. For example, reported is a process of condensing a pyridine compound and the N-oxide of another pyridine compound under heating in the presence of platinum-added Pd-C (Yakugaku Zasshi, 99(12), pp. 1176, 1181(1976)). The production yield is however low in this process. Also reported is cross-coupling reaction (Japanese Patent Laid-Open No. Sho 64-003169) making use of Grignard reaction, which is however accompanied with the such problems as difficulty in gaining or synthesizing a pyridine iodide compound necessary for obtaining a Grignard reagent of pyridines and necessity of special equipment.
In addition, proposed are Ullman condensation reaction of two pyridine halide compounds (Khim. Geol. Nauk., pp. 114(1970) and a process of cross-coupling a pyridine halide compound with a metal derivative in the presence of a Pd catalyst. For example, reported are cross-coupling with a borane derivative (Chem. Pharm. Bull., 33(11), pp. 4755(1985), Heterocycles, 23(9), pp. 2375(1985)), cross-coupling with an alkyl tin derivative (Tetrahedron Lett., 33, pp. 2199(1992)) and cross-coupling with a pyridine halide compound in the presence of an Ni catalyst (WO9852922).
For mass production, however, they involve many problems such as high cost of the catalyst or reagent employed for the reaction and necessity of special treatment for the metal waste. Moreover, existence of many byproducts of these reactions makes separation difficult and a product pure enough to use as an intermediate for pharmaceuticals or electron materials have not yet been obtained.
A process for synthesizing pyridine derivatives from a 1,2,4-triazine compound by using 2,5-norbornadiene is conventionally known (for example, Tetrahedron Lett., 39, pp. 8817, 8821, 8825 (1988)).
Upon use for mass production, however, 2,5-norbornadiene is accompanied with many problems that a large excess, more specifically, at least 10 equivalents is required relative to the amount of a substrate, reaction is not completed in a short time, it is expensive, it is so toxic that even slight suction of it causes headaches, and it has a problem in stable supply on an industrial scale.
A process for obtaining pyridine compounds by using 1,2,4-triazine and vinyl acetate is reported (Tetrahedron Lett., 59, pp. 5171(1969)), but its yield is low and in addition, a substrate usable for this process is limited to highly active 1,2,4-triazine having an alkoxycarbonyl group at the 3,5,6-positions.
An object of the present invention is to provide a process for producing high-purity pyridine derivatives useful as an intermediate of pharmaceuticals, agrichemicals or liquid crystals in a high yield and at a low cost, in which the process does not generate pollution problems and can be carried out on an industrial scale.
DISCLOSURE OF THE INVENTION
According to the present invention, the below-described processes for producing pyridine derivatives are provided and the above-described objet of the present invention is attained.
(1) A process for producing a pyridine derivative, which comprises reacting a 1,2,4-triazine compound with a vinyl carboxylate represented by the following formula (I):
wherein R represents an alkyl group having at least 3 carbon atoms, a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocyclic residue.
(2) The process for producing a pyridine derivative according to the item (1), wherein in the formula (I), R represents a alkyl group having 7 to 17 carbon atoms.
(3) The process for producing a pyridine derivative according to the item (1), wherein in the formula (I), R represents a substituted or unsubstituted phenyl group or a substituted or unsubstituted nitrogen-containing heterocyclic residue.
(4) The process for producing a pyridine derivative according to the item (1), which comprises reacting a 1,2,4-triazine compound represented by the following formula (III) with a vinyl carboxylate represented by the above-described formula (I):
wherein R1, R2 and R3 may be the same or different and each represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic residue, an alkylthio group, an alkylsulfinyl group, an alkylsulfonyl group, an arylsulfinyl group, an arylsulfonyl group, an alkoxy group, a phenoxy group, an alkoxycarbonyl group or a phenoxycarbonyl group; R2 and R3 may be coupled together to form a ring.
(5) The process for producing a pyridine derivative according to the item (4), wherein in the formula (III), R1 represents a phenyl group or a nitrogen-containing heterocyclic residue.
(6) The process for producing a pyridine derivative according to the item (1), wherein the vinyl carboxylate is used in an amount of 1.01 to 20 moles per mole of the 1,2,4-triazine compound.
(7) The process for producing a pyridine derivative according to the item (1), wherein the vinyl carboxylate is used in. an amount of 1.5 to 5 moles per mole of the 1,2,4-triazine compound.
(8) The process for producing a pyridine derivative according to the item (1), wherein a reaction solvent having a boiling point of 100° C. or greater is employed.
(9) The process for producing a pyridine derivative according to the item (1), wherein a reaction solvent having a boiling point of 180 to 250° C. is employed.
(10) A process for producing a pyridine derivative, which comprises reacting a 1,2,4-triazine compound with a vinyl carboxylate derivative represented by the following formula (II):
wherein n represents an integer of 0 to 18.
(11) The process for producing a pyridine derivative according to the item (10), wherein in the formula (II), n represents an integer of 3 to 12.
(12) The process for producing a pyridine derivative according to the item (10), which comprises reacting a 1,2,4-triazine compound represented by the following formula (III) with the vinyl carboxylate represented by the above-described formula (II):
wherein R1, R2 and R3 may be the same or different and each represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic residue, an alkylthio group, an alkylsulfinyl group, an alkylsulfonyl group, an arylsulfinyl group, an arylsulfonyl group, an alkoxy group, a phenoxy group, an alkoxycarbonyl group or a phenoxycarbonyl group; R2 and R3 may be coupled together to form a ring.
(13) The process for producing a pyridine derivative according to the item (12), wherein in the formula (III), R1 is a phenyl group or a nitrogen-containing heterocyclic residue.
(14) The process for producing a pyridine derivative according to the item (10), wherein the vinyl carboxylate is used in an amount of 0.505 to 10 moles per mole of the 1,2,4-triazine compound.
(15) The process for producing a pyridine derivative according to the item (10), wherein the vinyl carboxylate is used in an amount of 0.75 to 2.5 moles per mole of the 1,2,4-triazine compound.
(16) The process for producing a pyridine derivative according to the item (10), wherein a reaction solvent having a boiling point of 100° C. or greater is employed.
(17) The process for producing a pyridine derivative according to the item (10), wherein a reaction solvent having a boiling point of 180 to 250° C. is employed.
BEST MODE FOR CARRYING OUT THE INVENTION
The present invention will hereinafter be described more specifically.
In the vinyl carboxylate represented by the formula (I) or (II), R represents a linear, branched or cyclic alkyl group having at least 3 carbon atoms, a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocyclic residue. As the substituent for the aryl or heterocyclic residue, those havin

Affiliated with

Also associated with

Rating

Process for the production of pyridine derivatives does not yet have a rating. At this time, there are no reviews or comments for this patent.

If you have personal experience with Process for the production of pyridine derivatives, we encourage you to share that experience with our LandOfFree.com community. Your opinion is very important and Process for the production of pyridine derivatives will most certainly appreciate the feedback.

Rate now

Comments { 0 }

Profile ID: LFUS-PAI-O-3029305