2,6-DIHALO-5-ALKOXY-4-SUBSTITUTED-PIRIMIDINES, PIRIMIDINE-CARBALDEHIDES AND METHODS OF FORMATION AND USE Russian patent published in 2017 - IPC C07D239/34 C07D405/04 A01N43/54 A01P13/00 

FIELD: chemistry.

SUBSTANCE: invention relates to novel 2.6-dihalo-5-alkoxy-4-substituted pyrimidines of formula (I) and 2.6-dihalo-5-alkoxy-4-Pyrimidine carboxaldehydes formula (II), which can be used as intermediates for herbicides with a broad spectrum of activity in combating weeds. Describes these compounds as well as processes for their preparation and use thereof. In the compound of formula (I) X₁ is halogen; R₁ is selected from the group consisting of vinyl, alkenyl, and furyl; and Q represents a C₁-C₂ alkoxy. In the compound of formula II X1 is halo; and Q represents a C₁-C₂ alkoxy. The invention also relates to a process for the preparation of 2.6-dihalo-5-alkoxy-4-substituted-pyrimidine derivative of formula (I), wherein the substituent in position 4 of the pyrimidine ring is selected from the group consisting of vinyl, alkenyl, aryl and furyl. The process comprises reacting a 2.6-dihalo-5-alkoxy-pyrimidine with an organometallic reagent of a halide to form 2.6-dihalo-5-alkoxy-4-substituted-3-(metal-halogen or metal)-pyrimidine and oxidizing the resulting 2.6-dihalo-5-alkoxy-4-substituted-3-(metal-halogen or metal)-pyrimidine to form 2.6-dihalo-5-alkoxy-4-substituted-pyrimidine compound of formula (I). As the organometallic reagent is preferably used Grignard reagent such as vinyl magnesium bromide. In can also be used as the organometallic reagent is an organolithium reagent. For the oxidation of 2.6-dihalo-5-alkoxy-4-substituted-3-(metal-halogen or metal)-pyrimidine using 2.3-dichloro-5.6-dicyano-p-benzoquinone. A compound of formula (I), obtained above, wherein R1 is vinyl, can be converted to a compound (II) by oxidation with an oxidizing agent such as ozone. The resultant 2.6-dihalo-5-alkoxy-pyrimidin-carbaldehyde of formula (II) can be treated with bromine in an alcohol to obtain alkyl-2.6-dihalogeno-5-alkoxy-pyrimidin-4-carboxylate, and then treated with an amine to form alkyl-6-amino-2-halo-5-alkoxy-pyrimidin-4-carboxylate. Alternatively, the compound of formula (I), obtained above can be reacted with an amine to form 6-amino-2-halo-5-alkoxy-4-substituted-pyrimidine, wherein the substituent in position 4 of the pyrimidine ring is vinyl or furyl. The resulting compound, when the 6-amino-2-halo-5-alkoxy-4-substituted-pyrimidine substituent at position 4 of the pyrimidine ring is a vinyl, can be oxidized by an oxidizing agent to form a 6-amino-2-halo-5-alkoxy-pyrimidin-4-carbaldehyde. The obtained compound if necessary, can be treated with bromine in an alcohol to obtain alkyl-6-amino-2-halo-5-alkoxy-pyrimidin-4-carboxylate.

EFFECT: high effectiveness of compounds.

20 cl, 15 ex