Process for producing guanidine derivatives, intermediates there

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

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546329, 548203, 548205, 558 8, C07C27708, C07C27936, C07C27318, C07D27728, C07D21338, C07D20948

Patent

active

060083638

DESCRIPTION:

BRIEF SUMMARY
TECHNICAL FIELD

The present invention relates to a process for producing guanidine derivatives which are useful as insecticides, novel intermediates therefor, and a process for producing the intermediates.


BACKGROUND ART

EP-A 376279 corresponding to JP-A H3(1991)-157308, for instance, describes guanidine derivatives having pesticidal activity and a process for producing the derivatives. Moreover, as an improved production process for the guanidine derivatives, EP-A 452782 corresponding to JP-A H5(1993)-9173 discloses a production process via an isothiourea derivative having a cyclic diacyl group as shown in the following schema 1. ##STR2## wherein R.sub.1, R.sub.2, R.sub.4a, and R.sub.5a are the same or different, H or a hydrocarbon group which may optionally be substituted; A' is a divalent hydrocarbon group which may optionally be substituted; Q' is a heterocyclic group which may optionally be substituted; X' is an electron withdrawing group; Y.sub.1 and Y.sub.2 are the same or different, a leaving group; n is 0 or 1.
Furthermore, EP-A 375907 corresponding to JP-A H2(1990)-288860 discloses guanidine derivatives having pesticidal activity, and the following process for producing the derivatives. ##STR3## wherein R.sup.1' and R.sup.2' are hydrogen or C.sub.1-4 alkyl, R.sup.4' is C.sub.1-4 alkyl, Z is a five- or six-membered heterocyclic group having at least one nitrogen atom which may be substituted by halegen or C.sub.1-4 alkyl, R.sup.5' and R.sup.6' are hydrogen or C.sub.1-4 alkyl.
However, in these processes for producing the guanidine derivatives, there are some problems such that a mercaptan compound of RSH (wherein R is a hydrocarbon group which may optionally be substituted) having bad smell is formed as a by-product.
In the above state of the art, the object of present invention is to provide a process which is advantageous to an industrial mass production of guanidine derivatives in a higher yield by simple and convenient reaction procedures without bad smell, novel intermediates therefor, and a process for producing the intermediates.


DISCLOSURE OF INVENTION

To accomplish the above-mentioned object, the inventors of the present invention earnestly explored for a new production route to a guanidine derivative of the formula [I]: ##STR4## wherein R.sup.2 is H or a hydrocarbon group which may optionally be substituted; R.sup.3 is an amino group which may optionally be substituted; Q is a heterocyclic group which may optionally be substituted; X is an electron attracting group; n is 0 or 1.
As a result, the inventors discovered that an N-cyclodiacyl-N'-substituted isourea derivative of the formula [IV]: ##STR5## wherein R.sup.1 is a hydrocarbon group which may optionally be substituted, A is a divalent hydrocarbon group which may optionally be substituted, and X is as defined above, can be produced in high yield by reacting an N-substituted isourea derivative of the formula [II]: ##STR6## wherein the symbols are as defined above, or a salt thereof, with a compound of the formula [III]: ##STR7## wherein Y.sup.1 and Y.sup.2 are the same or different, a leaving group; A is as defined above.
The inventors further found that a compound of the formula [VI]: ##STR8## wherein the symbols are as defined above, or a salt thereof, can be produced in high yield by reacting the compound [IV] with a compound of the formula [V]:
Based on the above findings, the inventors did further research and found surprisingly that when the compound [VI] or a salt thereof is reacted with an amine or a salt thereof either in water or in a mixture of water and an organic solvent, the guanidine derivative [I] or a salt thereof is produced in high yield.
And, the inventors further found that the compound [VI] or a salt thereof can be produced by reacting the compound [II] or a salt thereof with the compound [V] or a salt thereof not via the compound [IV]. The inventors did further reseach and discovered to their own surprise that the compound [VI] or a salt thereof can be produced in a further improved yield by conducting t

REFERENCES:
patent: 5034404 (1991-07-01), Uneme et al.
patent: 5180833 (1993-01-01), Uneme et al.
patent: 5214152 (1993-05-01), Minamida et al.
patent: 5489603 (1996-02-01), Uneme et al.
Heyboer et al, Rec, Trav. Chim., vol. 81, pp. 69 to 72, 1962.

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