16018-87-4

Usage

Uses

5-Chloro-6-methyluracil is used in preparation of herbicide.

Synthesis Reference(s)

The Journal of Organic Chemistry, 26, p. 1874, 1961 DOI: 10.1021/jo01065a045

InChI:InChI=1/C5H5ClN2O2/c1-2-3(6)4(9)8-5(10)7-2/h1H3,(H2,7,8,9,10)

Upstream product

• 73742-45-7 5-chloro-6-(chloromethyl)-1,2,3,4-tetrahydropyrimidine-2,4-dione 
• 873422-37-8 5,5-dichloro-6-methoxy-6-methyl-5,6-dihydrouracil 
• 50610-49-6 5,5-dichloro-6-hydroxy-6-methyl-5,6-dihydrouracil 
• 626-48-2 6-Methyluracil 
• 1413433-45-0 5-bromo-5-chloro-6-hydroxy-6-methyl-5,6-dihydrouracil 
• 24048-74-6 1,2,3,4-tetrahydro-6-methyl-2,4-dioxo-5-pyrimidinecarbaldehyde 

Downstream Products

• 6554-69-4 6-Methyl-2,4,5-trichloropyrimidine 
• 93669-64-8 4,5-Dichloro-2-N-methylanilino-6-methylpyrimidine 
• 93669-69-3 5-Chloro-6-methyl-2,4-bis(N-methylanilino)pyrimidine 
• 93669-50-2 2,5-Dichloro-6-methyl-4-N-methylanilinopyrimidine 

Relevant academic research and scientific papers

Halogenation and nitration of 1-carboxymethyl-5-methyluracil. Halophilic reaction involving acetic anhydride

1-Carboxymethyl-5-halo-6-hydroxy-5-methyl-5,6-dihydrouracils and 1-carboxymethyl-6-hydroxy-5-methyl-5-mtro-5,6-dihydrouracils were synthesized for the first time by oxidative halogenation and nitration of 1-carboxymethyl-5-methyluracil. Dihydrouracil derivatives bearing a Br atom at position C(5) and a hydroxy group at position C(6) treated with Ac2O undergo deoxyhalogenation.

Electrophilic ipso-substitution in uracil derivatives

Treatment of 5-iodo-1,3,6-trimethyluracil with 50% H2SO 4 gives 1,3,6-trimethyluracil; with 5-bromo-1,3,6-trimethyluracil, a mixture of 1,3,6-trimethyluracil and 6-bromomethyl-1,3-dimethyluracil is obtained. 5-Chloro-1,3,6-trimethyluracil remains inert under these conditions. According to the DFT modeling of the reactions of 5-halo-1,3,6-trimethyluracils, a nucleophilic agent can abstract either Hal+ or the methyl proton from the carbocation formed by protonation of the starting halouracil at position 5, which accounts for the formation of two products from the 5-bromo derivative. Under similar conditions, 6-methyluracil dibromohydrin yields N-bromo-5-bromo-6-hydroxymethyluracil. Bromination or chlorination of 5-hydroxymethyl- or 5-formyl-6-methyluracils follows the ipso-substitution scheme leading to 6-methyluracil 5-halo- and 5,5-dihalohydrins.

Oxidative halogenation of 6-methyluracil

An efficient method has been developed for the preparation of halo derivatives of 6-methyluracil by employing oxidative halogenation. Elemental halogens and potassium halides were used as the halogenating agents, while NaNO3 and H2O2 were used as the oxidizing agents. Iodination of 6-methyl-uracil leads to 5-iodo-6-methyluracil as the single reaction product, while bromination or chlorination lead to 5-halo-6-methyluracil, 5,5-dihalo-6-hydroxy-6-methyl-5,6-dihydrouracil, or their mixture depending on the acidity of the medium and the ratio of the substrate and reagents. Bromination of 5-chloro-6-methyluracil leads to 5-bromo-5-chloro-6-hydroxy-6-methyl-5,6-dihydrouracil, while chlorination of 6-methyl-, 5-bromo-6-methyl-, and 5-chloro-6-methyluracils using gaseous chlorine yields 5,5-dichloro-6-hydroxy-6-methyl-5,6-dihydrouracil.