22114-32-5

Upstream product

• 5764-82-9 bromo(2-ethoxy-2-oxoethyl)zinc 
• 16879-39-3 2-bromo-4,6-dimethylpyrimidine 
• 16879-40-6 2-iodo-4,6-dimethylpyrimidine 
• 124-09-4 1,6-Hexanediamine 
• 140-87-4 Cyanoacetohydrazide 
• 1068-57-1 acetic acid hydrazide 
• 77-86-1 2-amino-2-hydroxymethyl-1,3-propanediol 
• 622849-35-8 2-ethoxycarbonylmethyl-2-hydroxy-1,4,6-trimethyl-1,2-dihydropyrimidine 
• 74-89-5 methylamine 
• 100-46-9 benzylamine 
• 141-43-5 ethanolamine 
• 619-67-0 4-Hydrazinobenzoic acid 
• 371118-71-7 methyl 3-(3-methyl-1H-pyrazol-1-yl)propionate 
• 56563-02-1 2-(1H-1,2,4-triazol-1-yl)acetohydrazide 

Downstream Products

• 80601-98-5 4,6-Dimethyl-2-pyrimidinylacetic acid anilide 

Relevant academic research and scientific papers

Synthesis of N- and C-azolyl-substituted pyrazolo[1,5-a]pyrimidines by recyclization of pyrimidinium salts

We studied the reaction of 2-(ethoxycarbonyl)methyl-1,4,6-trimethylpyrimidinium iodide with hydrazides of N-azolyl- and C-pyrazolyl-substituted carboxylic acids, which were synthesized by reacting the respective esters with hydrazine hydrate. This reaction was shown to result in recyclization and formation of ethyl 2-(pyrazolylalkyl)- and 2-(azolylalkyl)-5,7-dimethylpyrazolo[1,5-a]pyrimidine- 3-carboxylates. Besides pyrazolopyrimidines, the separation of reaction mixture provided in some cases also another recyclization product, 2-hydroxy-5,7-dimethylpyrazolo[1,5-a]pyrimidine.

Recyclization of pyrimidinium salts into 1,2,4-triazole derivatives

The interaction of the iodomethylates of pyrimidinyl-2-acetic acid derivatives with monosubstituted hydrazines, in addition to the products of a Kost-Sagitullin rearrangement, leads also to N-substituted triazoles. The structure of the triazoles was demonstrated by NOESY NMR experiments. The structure of the reaction products was determined on the basis of the response observed in the spectra between the methyl group protons of the triazole ring and the spatially close proton of the substituent in position 1 and a conclusion was drawn on the direction of the primary attack of nucleophile in the recyclization process of the pyrimidinium salts into a 1,2,4-triazole.

Intermediates in the transformation of 1,2-dialkylpyrimidinium iodides in the Kost-Sagitullin rearrangement

Intermediate recyclization products were obtained in a study of the Kost-Sagitullin rearrangement of a series of 1,2-dialkylpyrimidinium iodides. The initial attack of the nucleophile leads to the formation of products of the addition of the hydroxyl group, namely, the corresponding pseudo bases. Heating one of these intermediates in ethanol or in the presence of primary amines leads to rearrangement to give a pyridone derivative. Upon heating in chloroform, the pseudo bases readily lose a water molecule and are converted to anhydro bases, namely, derivatives of 1-alkyl-1,2-dihydro-2-methylidenepyrimidine.

Novel route for the transformation of a pyrimidine ring using hydrazides

It has been shown from X-ray structural analytical data that the reaction of 2-ethoxycarbonylmethyl-1,4,6-trimethylpyrimidinium iodide with carboxylic acid hydrazides gives pyrazolo[1,5-a]pyrimidine derivatives and not the isomeric triazolo[4,3-a]pyridines previously reported. This novel and previously unreported rearrangement of 1,2-dialkylpyrimidinium salts occurs via recyclization of the pyrimidine ring with inclusion of a fragment of the nucleophilic reagent into the transformation product. 2006 Springer Science+Business Media, Inc.

Synthesis of nicotinic acid derivatives by the reaction of salts of 1-alkyl-4,6-dimethyl-2-pyrimidinylacetic acid esters with amines

A study was carried out on the enamine rearrangement of iodoalkylates of the ethyl ester of 4,6-dimethyl-2-pyrimidinylacetic acid to give ethyl esters of 2-alkylamino-4,6-dimethylnicotinic acid, which proceeds upon the action of various amines. The reaction with amines containing an alkyl substituent different from that at the quaternized nitrogen atom of the pyrimidinium salt leads to the formation of products of rearrangement and transamination. In the presence of water, the rearrangement is accompanied by the formation of the ethyl ester of 1,2-dihydro-2-oxo-4,6-dimethylnicotinic acid.

Exchange aminations in conversions of pyrimidinium iodides to 2- alkylaminonicotinic acids

1-Alkyl-2-(ethoxycarbonylmethyl)pyrimidinium iodides (1) are transformed into 2-alkylaminonicotinic acids (2) by reactions with aliphatic primary amines. Two alternative reaction paths are proposed, one of which involves exchange of the amine moieties.

Studies on Pyrimidine Derivatives. XXXVIII. Cross-Coupling Reaction of N-Heteroaryl Iodides with Ethoxycarbonylmethylzinc Bromide in the Presence of Palladium Catalyst

In the presence of tetrakis(triphenylphosphine)palladium, 2-iodo-4,6-dimethylpyrimidine and 4-iodo-2,6-dimethylpyrimidine reacted with ethoxycarbonylmethylzinc bromide (Reformatsky reagent) to give ethyl 4,6-dimethyl-2-pyrimidineacetate and ethyl 2,6-dimethyl-4-pyrimidineacetate, respectively.In contrast, the reaction of 5-iodo-2,4-dimethylpyrimidine with the same reagent resulted in recovery of the starting iodide.Similar results were observed in the reactions of various N-heteroaryl iodides.Keywords - Reformatsky reagent; cross-coupling reaction; N-heteroaryl halide; N-heteroarylacetic acid; palladium catalyst; ethyl bromoacetate