Process for producing pyridinecarboxamides or thiocarboxamides

Organic compounds -- part of the class 532-570 series – Organic compounds – Heterocyclic carbon compounds containing a hetero ring...

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Details

546323, C07D21381, C07D21382, C07D21383

Patent

active

060051124

DESCRIPTION:

BRIEF SUMMARY
TECHNICAL FIELD

The present invention relates to a process for producing N-substituted pyridine carboxamide or thiocarboxamide, and more particularly, it relates to an industrially useful process for producing N-substituted pyridine carboxamide or thiocarboxamide.


BACKGROUND ART

It is known that N-substituted-6-pyridine carboxamide or thiocarboxamide has a herbicidal activity, as described, for example, in Japanese Patent Application Laid-open (KOKAI) No. 4-290805, U.S. Pat. No. 4,270,946 or the like. As the most ordinary method for producing the above-mentioned compounds, there is known a method comprising producing a carboxylic acid, halogenating the carboxylic acid and then reacting the halogenated carboxylic acid with amine. In the above Japanese Patent Application Laid-open (KOKAI) No. 4-290805, it is described that pyridine carboxylic acid is produced by such an oxidation reaction of methyl pyridine as described in "J. Pharm. Belg." (1980), 35, 1, 5-11.
However, it has been difficult to produce the pyridine carboxylic acid having an oxidation-susceptible substituent group bonded to a pyridine ring thereof, such as an alkyl group, an amino group or a group having thiol ether bond, by the oxidation reaction such as oxidation of a methyl group with a high yield.
In addition, there is conventionally unknown any method of producing N-substituted pyridine thiocarboxamide without sulfidization of N-substituted pyridine carboxamide, until the process according to the present invention has been proposed herein by the present inventors.
The present invention has been attained in view of the above-mentioned problems. It is an object of the present invention to provide a industrially useful process for producing N-substituted pyridine carboxamide or thiocarboxamide, which can reduce limitations to production thereof.
As a result of the present inventors' earnest studies concerning a novel process for the production of N-substituted pyridine carboxamide or thiocarboxamide, it has been found that by reacting a pyridine metal compound and substituted isocyanate (or isothiocyanate) with each other, the aimed products, even N-substituted pyridine carboxamide having an oxidation-susceptible substituent group, can be produced with a high yield, and N-substituted pyridine thiocarboxamide can be produced with a high yield without sulfidization of N-substituted pyridine carboxamide. The present invention has been attained on the basis of the finding.


DISCLOSURE OF THE INVENTION

That is, in an aspect of the present invention, there is provided a process for producing N-substituted pyridine carboxamide or thiocarboxamide, comprising reacting a pyridine metal compound with substituted isocyanate (or thioisocyanate) to obtain an addition reaction product thereof, and then substituting the metal of the addition reaction product with a proton.
The present invention is described in detail below. In the present invention, N-substituted pyridine carboxamide or thiocarboxamide can be usually produced by reacting a pyridine metal compound with a substituted isocyanate or thioisocyanate (in the present specification, which means not only compounds expressed by the terminology "substituted isocyanate or thioisocyanate", especially those represented herein by the specific chemical formulae, but also compounds to which at least one isocyanate or thioisocyanate group is bonded) to obtain an addition reaction product thereof, and then substituting the metal of the addition reaction product with a proton. The above-mentioned pyridine metal compound and substituted isocyanate or thioisocyanate are not limited to particular ones as far as N-substituted pyridine carboxamide or thiocarboxamide can be produced therefrom by the process according to the present invention.
As the substituent groups of the above-mentioned pyridine metal compounds, there may be usually exemplified a halogen atom, an alkyl group, a haloalkyl group, an alkoxy group, a haloalkoxy group, an alkylthio group, a haloalkylthio group, a dialkylamino group, a (substitu

REFERENCES:
patent: 3505344 (1970-04-01), Kelyman
patent: 4270946 (1981-06-01), Gutman

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