Yu. Yu. Mayakova

Synthesis of alkyl methyl ethers and alkyl methyl carbonates by reaction of alcohols with dimethyl carbonate in the presence of tungsten and cobalt complexes

Alkyl methyl ethers and alkyl methyl carbonates were synthesized by reaction of alcohols with dimethyl carbonate in the presence of tungsten and cobalt carbonyls. Optimal reactant and catalyst ratios, as well as reaction conditions, were found for selective formation of alkyl methyl ethers or alkyl methyl carbonates.

Amidation of Adamantane and Diamantane with Acetonitrile and Bromotrichloromethane in the Presence of Mo(CO) 6 in Aqueous Medium

N-(1-Adamantyl)acetamide and its derivatives are starting compounds in the synthesis of biologically active aminoadamantanes possessing antimicrobial and antiviral activity and used in the treatment and prophylactics of influenza, herpes, and pneumonia. Removal of acetyl protection from N-(1-adamantyl)acetamide yields 1-aminoadamantane which is the active component of the known drug midantane for the treatment of Parkinson’s disease [1–5].

Methylation of mono- and dicarboxylic acids with dimethyl carbonate catalyzed with binder-free zeolite NaY

Synthesis of methyl mono- and dicarboxylates was developed consisting in treating the corresponding acids with dimethyl carbonate in the presence of a heterogenic catalyst, crystalline aluminosilicate whose mechanically strong granules to 90–95% were built of crystal aggregates of zeolite Y with modulus of about 5.0 in the Na-form. Optimum catalyst and reagents ratio and the reaction conditions were found for the preparation in high yields of methyl esters of mono- and dicarboxylic acids.

Ritter reaction of organic nitriles with 1-bromo- and 1-hydroxyadamantanes catalyzed by manganese compounds and complexes

Manganese compounds and complexes [MnCl2, MnBr2, Mn(OAc)2, Mn(acac)2, Mn(acac)3, Mn2(CO)10] catalyze Ritter reaction of organic nitriles with 1-bromo- and 1-hydroxyadamantanes. The reaction proceeds in water environment in the absence of acids at 100–130°C over 3–5 h and affords N-(adamantan-1-yl)amides in 75–100% yields.

Synthesis of 2-thiophenecarboxylic and 2,5-thiophenedicarboxylic acid esters via the reaction of thiophenes with the CCl4-ROH reagent in the presence of vanadium, iron, and molybdenum catalysts

Abstract2-Thiophenecarboxylic and 2,5-thiohenedicarboxylic acid esters were synthesized via the reaction of thiophene with the CCl4-ROH-catalyst system, with a total yield of 44–85%. A possible reaction scheme includes the successive steps of alkylation of thiophene with carbon tetrachloride, leading to 2-trichloromethylthiophene, and alcoholysis of the product giving the corresponding 2-thiophenecarboxylate. The best catalysts for this reaction are VO(acac)2, Fe(acac)3, and Mo(CO)6.

Chlorination of hydrocarbons with CCl4 catalyzed by complexes of Mn, Mo, V, Fe

Catalytic chlorination of alkanes, cycloalkanes, and adamantane utilizing tetrachloromethane as the source of chlorine and applying catalysts containing manganese, molybdenum, vanadium, and iron activated with nitrile ligands, alcohols, and water was fulfilled. The optimum ratios of catalysts and reagents and the best reaction conditions were found for selective synthesis of chlorine-substituted hydrocarbons derivatives.

Methylation of aniline and its derivatives with dimethyl carbonate in the presence of binder-free micro-, meso-, and macroporous zeolites KNaX, NaY, and HY

Aniline and its derivatives undergo methylation when treated with dimethyl carbonate in the presence of binder-free micro-, meso-, and macroporous zeolites KNaX, NaY, and HY leading to the formation of N-methyl- and N,N-dimethylanilines.

Methylation of phenol and its derivatives with dimethyl carbonate in the presence of Mn2(CO)10, W(CO)6, and Co2(CO)8

Aryl methyl ethers were synthesized by reactions of phenol, substituted phenols, and α- and β-naphthols with dimethyl carbonate in the presence of manganese, tungsten, and cobalt carbonyls. Optimal reactant and catalyst ratios and reaction conditions were found to ensure selective formation of aryl methyl ethers.

Molybdenum hexacarbonyl-catalyzed condensation of malononitrile with ketones and aldehydes

Molybdenum hexacarbonyl activated with pyridine or morpholine catalyzes the condensation of malononitrile with ketones and aldehydes at 140 °C, which leads to alkylidenemalononitriles in 75–100% yield.

Unusual reaction of adamantane-1-carboxylic acid and adamantane-1-carbonyl chloride with acetonitrile and carbon tetrachloride in the presence of VO(acac)2

The presence of an electron-withdrawing group at the bridgehead position of adamantane molecule is known to considerably reduce its reactivity in substitution reactions, for that substituent somewhat restricts introduction of a second functional group into the adamantane core. This relation is clearly demonstrated by the reactions of adamantane-1-carboxylic acid (I) with PCl3 and SOCl2, which lead to the formation of adamantane-1-carbonyl chloride (II) instead of chlorination at the skeletal carbon atoms [1]. The chlorination of adamantane-1-carbonyl chloride (II) with the use of AlCl3 resulted in replacement of the COCl group with formation of 1-chloroadamantane [2]. Disubstituted adamantane derivatives containing a halogen atom together with another electronwithdrawing group are usually prepared via multistep procedures [3, 4]. We now report on simultaneous chlorination at the bridgehead position and replacement of the COOH or COCl group by cyano in adamantane-1-carboxylic acid (I) or adamantane-1-carbonyl chloride (II) by the action of carbon tetrachloride and acetonitrile in the presence of vanadyl acetoacetonate VO(acac)2 as catalyst. The product of this reaction was 3-chloroadamantane-3-carbonitrile (III) (Scheme 1). The reaction time depended on the temperature. The reaction carried out at 125°C was complete in 3 h, at 140°C in 1.5 h, and at 150°C in 1 h. Prolonged heating of the reactants in the presence of VO(acac)2 is undesirable because of tarring. Regardless of the initial compound (I or II), the second product was chloroform, i.e., the chlorinating agent is carbon tetrachloride. Excess carbon tetrachloride also acts as solvent. No reaction occurred in the absence of CCl4. The molar reactant ratio VO(acac)2–AdR–CCl4–MeCN was 1 : (100–1000) : (200–2000) : (100–1000). High efficiency of the process and low consumption of the catalyst should be noted.