Preparation of fungicidal quinazolinones and useful intermediate

Details Preparation of fungicidal quinazolinones and useful intermediate Preparation of fungicidal quinazolinones and useful intermediate

1998-12-09

2000-12-26

Raymond, Richard L.

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

Organic compounds

Nitrogen attached directly or indirectly to the purine ring...

C07D23996, C07C27168

Patent

active

061662089

DESCRIPTION:

BRIEF SUMMARY
FIELD OF THE INVENTION

This invention relates to compounds and processes for the preparation of fungicidal quinazolinones.


BACKGROUND OF THE INVENTION

WO 94/26722 generically discloses conversion of anthranilic acids to 2-thioquinazolinediones with isothiocyanates (see also: U.S. Pat. No. 3,755,582). WO 94/26722 discloses that the reaction is preferably performed in the presence of a base such as triethylamine.
WO 94/26722 also discloses conversion of 2-thioquinazolinediones to 2-chloro-4(3H)-quinzolinones using sulfuryl chloride (see also: U.S. Pat. No. 3,867,384). No mention is made of using phosgene for this transformation.
WO 94/26722 and U.S. Pat. No. 3,755,582 generically disclose 2-alkylthio-quinazolinones.
WO 94/26722 generically discloses the condensation of anthranilic acid esters with thiophosgene to form isothiocyanate esters. Similar procedures are disclosed in J. Heterocycl. Chem., (1990), 27, 407.
The preparation of 2,4-(1H,3H)-quinazolinediones from anthranilic acid and esters plus isocyanates is cited in J. Heterocycl. Chem., (1982), 19, 269.
EP-A-712849 discloses a process for the preparation of quinazoline-2,4-diones.


SUMMARY OF THE INVENTION

This invention provides advantageous processes for preparing quinazolinones of Formula I ##STR4## wherein: R.sup.1 is C.sub.1 -C.sub.10 alkyl; C.sub.3 -C.sub.10 alkenyl; C.sub.3 -C.sub.10 cycloalkyl; C.sub.3 -C.sub.10 halocycloalkyl; C.sub.4 -C.sub.10 cycloalkylalkyl; C.sub.4 -C.sub.10 halocycloalkylalkyl; or C.sub.3 -C.sub.10 alkynyl; -C.sub.10 cycloalkyl; C.sub.3 -C.sub.10 halocycloalkyl; C.sub.4 -C.sub.10 cycloalkylalkyl; C.sub.4 -C.sub.10 halocycloalkylalkyl; C.sub.4 -C.sub.10 cycloalkyl; C.sub.4 -C.sub.10 halocycloalkyl; or C.sub.3 -C.sub.10 alkynyl; and R.sup.3 and R.sup.4 are each independently hydrogen or halogen; from compounds containing the moiety IIg ##STR5##
The quinazolinones of Formula I are useful as fungicides and/or intermediates for preparing fungicides. The processes for preparing the quinazolinones of Formula I provided herein are characterized by employing a process sequence (A-E) as described below.
One process for preparing compounds of Formula I is provided which comprises (a) treating a 2-thioquinazolinedione of Formula IIa ##STR6## with phosgene in an inert solvent, at a temperature from about 50 to 120.degree. C., and a pressure of from about 1 to 5 atmospheres (1.013.times.10.sup.5 to 5.065.times.10.sup.5 Pa), to form a 2-chloro-4(3H)-quinazolinone of Formula IIb ##STR7## and (b) treating the 2-chloro-4(3H)-quinazolinone with a metal alkoxide of Formula M.sup.+ (.sup.- OR.sup.2) wherein M is lithium, sodium or potassium, in an inert solvent, at a temperature of from about -20 to 50.degree. C., and a pressure of from about 1 to 5 atmospheres (1.013.times.10.sup.5 to 5.065.times.10.sup.5 Pa).
Another process for preparing compounds of Formula I is provided which comprises treating a quinazolinedione of Formula IIc ##STR8## with an alkylating agent of the formula R.sup.2 --Z where Z is iodide, bromide, chloride, alkyl sulfonate, aryl sulfonate, sulfate, or oxonium tetrafluoroborate in an inert solvent at a temperature of from about 25 to 110.degree. C. and a pressure of from about 1 to 5 atmospheres (1.013.times.10.sup.5 to 5.065.times.10.sup.5 Pa).
The quinazolinedione of Formula IIc may be prepared by (a1) contacting an isatoic anhydride of Formula 2 ##STR9## with a primary amine of the formula R.sup.1 --NH.sub.2 to form the aminobenzamide of Formula 3 ##STR10## and (b I) treating the aminobenzamide of Formula 3 with phosgene in an inert solvent at a temperature of from about 20 to 1 20.degree. C. and a pressure of from about 1 to 5 atmospheres (1.013.times.10.sup.5 to 5.065.times.10.sup.5 Pa) to form the quinazolinedione of Formula IIc, or by (a2) reacting a compound of Formula 1b ##STR11## wherein R.sup.6 is hydrogen or C.sub.1 -C.sub.6 alkyl with an isocyanate of the formula R.sup.1 --N.dbd.C.dbd.O in a suitable solvent and (b2) distilling the solvent and heating the neat residue at temperatures ranging from abo

REFERENCES:
patent: 3755582 (1973-08-01), Bullock
patent: 3867384 (1975-02-01), Bullock et al.
William D. Dean et al., Synthesis of 4(3H)-Quinazolinones from Derivatives of Methyl-2-Isothiocyanatobenzoate, J. Heterocyclic Chem., 19, 1117-1123, Sep.-Oct. 1982.
Chemical Abstracts, 107, No. 25, Abstract No. 228515k, re. R. Lakhan, et al., Studies of 4(3H)Quinazolinone Derivatives, 1987.
Chemical Abstracts, 89, No. 13, Abstract No. 109345e re. P. Bhargava et al., Synthesis of 6,8-Diiodo-S-Substit.2Thio-3-Aryl(alkyl)-4(3H)-quinazolinones,, 1978.
Urleb et al., The Synthesis and Transformation of 2-Ethoxycarbonyl-3-IsothiocyanaTopyridine, Pyrido[3,2-d]pyrimidines and some Azolopyridol[3,2-d]pyrimidines, J. Heterocycl. Chem. (27) 407 (1990).
E.P. Papadopoulos et al, Convenient Preparation of N-Substituted 2-Amino-4H-3,1-benzoxazin-4-Ones and 3-Substituted 2,4(1H,3H)-Quinazolinediones,, J. Heterocycl. Chem., (19) 269 (1982).

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