Process for making oximes and use thereof to prepare cyclic urea fungicides

Abstract

An advantageous process for preparing agriculturally suitable precursor compositions containing a compound of Formula IV is disclosed. The process involves (a) reacting a compound of Formula V with a nitrosating agent to provide a diazonium ion of Formula Va, (b) reacting the diazonium ion with a compound of Formula VI in the presence of a copper salt catalyst to obtain a reaction product containing the compound of Formula IV and greater than 100 ppm copper (based on the weight of Formula IV compound), and (c) separating copper from the Formula IV compound to obtain a purified product composition containing the compound of Formula IV and less than 10 ppm copper (based on the weight of Formula IV compound). ##STR1## A method for preparing a cyclic urea fungicides of Formula I is disclosed, which involves (1) preparing an agriculturally suitable precursor composition as indicated (2) reacting the oxime of Formula IV from said precursor composition with a compound of Formula III to provide a compound of Formula II, and (3) reacting the compound of Formula II with a compound of Formula MOR.sup.1. ##STR2## Suitable R.sup.1 -R.sup.5, R.sup.7, R.sup.8 and Lg are indicated in the specification.

Claims

1. A process for preparing an agriculturally suitable precursor composition containing a compound of Formula IV ##STR15## wherein R.sup.2 is H; C.sub.1 -C.sub.6 alkyl; C.sub.1 -C.sub.6 haloalkyl; C.sub.1 -C.sub.6 alkoxy; C.sub.1 -C.sub.6 haloalkoxy; C.sub.1 -C.sub.6 alkylthio; C.sub.2 -C.sub.6 alkenyl; C.sub.2 -C.sub.6 haloalkenyl; C.sub.2 -C.sub.6 alkynyl; C.sub.2 -C.sub.6 haloalkynyl; C.sub.3 -C.sub.6 cycloalkyl; C.sub.2 -C.sub.4 alkylcarbonyl; C.sub.2 -C.sub.4 alkoxycarbonyl; cyano; or morpholinyl;

R.sup.7 is H; 1-2 halogen; C.sub.1 -C.sub.6 alkyl; C.sub.1 -C.sub.6 haloalkyl; C.sub.1 -C.sub.6 alkoxy; C.sub.1 -C.sub.6 haloalkoxy; C.sub.2 -C.sub.6 alkenyl; C.sub.2 -C.sub.6 haloalkenyl; C.sub.2 -C.sub.6 alkynyl; C.sub.1 -C.sub.6 alkylthio; C.sub.1 -C.sub.6 haloalkylthio; C.sub.1 -C.sub.6 alkylsulfinyl; C.sub.1 -C.sub.6 alkylsulfonyl; C.sub.3 -C.sub.6 cycloalkyl; C.sub.3 -C.sub.6 alkenyloxy; CO.sub.2 (C.sub.1 -C.sub.6 alkyl); NH(C.sub.1 -C.sub.6 alkyl); N(C.sub.1 -C.sub.6 alkyl).sub.2; --C(R.sup.11).dbd.NOR.sup.12; cyano; nitro; SiR.sup.13 R.sup.14 R.sup.15; GeR.sup.13 R.sup.14 R.sup.15; or R.sup.7 is phenyl, benzyl, benzoyl, phenoxy, pyridinyl, pyridinyloxy, thienyl, thienyloxy, furanyl, pyrimidinyl, or pyrimidinyloxy each optionally substituted with one of R.sup.9, R.sup.10, or both R.sup.9 and R.sup.10;

R.sup.8 is H; halogen; C.sub.1 -C.sub.4 alkyl; C.sub.1 -C.sub.4 haloalkyl; C.sub.1 -C.sub.4 alkoxy; nitro; or cyano;

R.sup.9 and R.sup.10 are each independently halogen; C.sub.1 -C.sub.4 alkyl; C.sub.1 -C.sub.4 haloalkyl; C.sub.1 -C.sub.4 alkoxy; C.sub.1 -C.sub.4 haloalkoxy; nitro; or cyano;

R.sup.11 and R.sup.12 are each independently H; C.sub.1 -C.sub.3 alkyl; or phenyl optionally substituted with halogen, C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 haloalkyl, C.sub.1 -C.sub.4 alkoxy, C.sub.1 -C.sub.4 haloalkoxy, nitro or cyano; and

R.sup.13, R.sup.14, and R.sup.15 are each independently C.sub.1 -C.sub.6 alkyl; C.sub.1 -C.sub.6 alkenyl; C.sub.1 -C.sub.4 alkoxy; or phenyl, comprising:

(a) reacting a compound of Formula V ##STR16## with a nitrosating agent to provide a diazonium ion of Formula Va ##STR17## (b) reacting the diazonium ion of Formula Va with a compound of Formula VI ##STR18## in the presence of a copper salt catalyst to obtain a reaction product containing the compound of Formula IV and greater than 100 ppm copper based on the weight the Formula IV compound; and

(c) separating copper from the Formula IV compound to obtain a purified product composition containing the compound of Formula IV and less than 10 ppm copper based on the weight of the Formula IV compound.

2. A method for preparing a cyclic urea fungicide, in particular, a cyclic urea fungicides of Formula I ##STR19## wherein R.sup.1 is C.sub.1 -C.sub.6 alkyl; C.sub.1 -C.sub.6 haloalkyl; C.sub.2 -C.sub.6 alkenyl; C.sub.2 -C.sub.6 haloalkenyl; C.sub.2 -C.sub.6 alkynyl; C.sub.2 -C.sub.6 haloalkynyl; or C.sub.3 -C.sub.6 cycloalkyl.

R.sup.2 is H; C.sub.1 -C.sub.6 alkyl; C.sub.1 -C.sub.6 haloalkyl; C.sub.1 -C.sub.6 alkoxy; C.sub.1 -C.sub.6 haloalkoxy; C.sub.1 -C.sub.6 alkylthio; C.sub.2 -C.sub.6 alkenyl; C.sub.2 -C.sub.6 haloalkenyl; C.sub.2 -C.sub.6 alkynyl; C.sub.2 -C.sub.6 haloalkynyl; C.sub.3 -C.sub.6 cycloalkyl; C.sub.2 -C.sub.4 alkylcarbonyl; C.sub.2 -C.sub.4 alkoxycarbonyl; cyano; or morpholinyl;

R.sup.3 and R.sup.4 are each independently H; halogen; cyano; nitro; C.sub.1 -C.sub.6 alkyl; C.sub.1 -C.sub.6 haloalkyl; C.sub.2 -C.sub.6 alkenyl; C.sub.2 -C.sub.6 haloalkenyl; C.sub.2 -C.sub.6 alkynyl; C.sub.2 -C.sub.6 haloalkynyl; C.sub.1 -C.sub.6 alkoxy; C.sub.1 -C.sub.6 haloalkoxy; C.sub.2 -C.sub.6 alkenyloxy; C.sub.2 -C.sub.4 alkoxycarbonyl; or C.sub.2 -C.sub.6 alkynyloxy;

R.sup.5 is H; or C.sub.1 -C.sub.3 alkyl;

R.sup.7 is H; 1-2 halogen; C.sub.1 -C.sub.6 alkyl; C.sub.1 -C.sub.6 haloalkyl; C.sub.1 -C.sub.6 alkoxy; C.sub.1 -C.sub.6 haloalkoxy; C.sub.2 -C.sub.6 alkenyl; C.sub.2 -C.sub.6 haloalkenyl; C.sub.2 -C.sub.6 alkynyl; C.sub.1 -C.sub.6 alkylthio; C.sub.1 -C.sub.6 haloalkylthio; C.sub.1 -C.sub.6 alkylsulfinyl; C.sub.1 -C.sub.6 alkylsulfonyl; C.sub.3 -C.sub.6 cycloalkyl; C.sub.3 -C.sub.6 alkenyloxy; CO.sub.2 (C.sub.1 -C.sub.6 alkyl); NH(C.sub.1 -C.sub.6 alkyl); N(C.sub.1 -C.sub.6 alkyl).sub.2; --C(R.sup.11).dbd.NOR.sup.12; cyano; nitro; SiR.sup.13 R.sup.14 R.sup.15; GeR.sup.13 R.sup.14 R.sup.15; or R.sup.7 is phenyl, benzyl, benzoyl, phenoxy, pyridinyl, pyridinyloxy, thienyl, thienyloxy, furanyl, pyrimidinyl, or pyrimidinyloxy each optionally substituted with one of R.sup.9, R.sup.10, or both R.sup.9 and R.sup.10;

R.sup.8 is H; halogen; C.sub.1 -C.sub.4 alkyl; C.sub.1 -C.sub.4 haloalkyl; C.sub.1 -C.sub.4 alkoxy; nitro; or cyano;

R.sup.9 and R.sup.10 are each independently halogen; C.sub.1 -C.sub.4 alkyl; C.sub.1 -C.sub.4 haloalkyl; C.sub.1 -C.sub.4 alkoxy; C.sub.1 -C.sub.4 haloalkoxy; nitro; or cyano;

R.sup.11 and R.sup.12 are each independently H; C.sub.1 -C.sub.3 alkyl; or phenyl optionally substituted with halogen, C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 haloalkyl, C.sub.1 -C.sub.4 alkoxy, C.sub.1 -C.sub.4 haloalkoxy, nitro or cyano; and

R.sup.13, R.sup.14, and R.sup.15 are each independently C.sub.1 -C.sub.6 alkyl; C.sub.1 -C.sub.6 alkenyl; C.sub.1 -C.sub.4 alkoxy; or phenyl, comprising

(1) preparing an agriculturally suitable precursor composition in accordance with claim 1;

(2) reacting the oxime of Formula IV from said precursor composition with a compound of Formula III ##STR20## wherein Lg is halogen; acetoxy; OSO.sub.2 Q or OP(OR.sup.16).sub.2;

Q is C.sub.1 -C.sub.6 alkyl; C.sub.1 -C.sub.6 haloalkyl; or phenyl optionally substituted with C.sub.1 -C.sub.3 alkyl; and

R.sup.16 is C.sub.1 -C.sub.6 alkyl; C.sub.1 -C.sub.6 alkenyl; or phenyl;

to provide a compound of Formula II ##STR21## and (3) reacting the compound of Formula II with a compound of the Formula MOR.sup.1, wherein M is lithium, sodium or potassium to form the cyclic urea fungicide of Formula I.