Yu. N. Ogibin

Synthesis of peroxide compounds by the BF3-catalyzed reaction of acetals and enol ethers with H2O2

Aliphatic and alicyclic gem-bis-hydroperoxides and their derivatives, bis(1-hydroperoxycycloalkyl) and bis(1-hydroperoxyalkyl) peroxides, dispiro- and tetraalkyl-1,2,4,5-tetroxanes were synthesized by the reaction of aliphatic and alicyclic acetals and enol ethers with H2O2 in the presence of BF3 in anhydrous Et2O.

Synthesis of nine-, ten-, and fifteen-membered alkenolides by the oxidative cleavage of the bridging C=C bond in 2-oxabicycloalkenes

Hydroperoxidation of C=C-bridged 2-oxabicycloalkenes in which the five- or six-membered oxacycle is fused with the five-, six-, or twelve-membered hydrocarbon ring was studied. The Cu(OAc)2-catalyzed decomposition of the resulting hydroperoxides afforded nine-, ten-, or fifteen-membered trans-alkenolides, respectively. The latter compounds were obtained as pairs of regioisomers, with the isomers in which the double bond is more remote from the ether oxygen atom predominating.

THE EFFECT OF ELECTROLYSIS CONDITIONS ON THE OXIDATION OF STYRENE IN METHANOL

Anodic oxidation of styrene (1) in methanol and the effect of the anion of the supporting electrolyte and of the anode material on this process have been studied. The most efficient conversion of1 into (1,2-dimethoxyethyl)benzene (2) occurs when the electrolysis is carried out with a platinum anode and with potassium fluoride or tetrabutylammonium tetrafluoroborate as the supporting electrolyte. Cleavage of the C-C σ bond in2 to give benzaldehyde dimethylacetal (3) is the most efficient at a graphite anode in the presence of sodium tosylate.

Synthesis of 1,1-bishydroperoxydi(cycloalkyl) peroxides by homocoupling of 11-15-membered gem-bis(hydroperoxy)cycloalkanes in the presence of boron trifluoride

A procedure was developed for the synthesis of 1,1′-bishydroperoxydi(C11-C15-cycloalkyl) peroxides based on homocoupling of geminal 11–15-membered bis(hydroperoxy)cycloalkanes in the presence of BF3⋅OEt2.

A new property of geminal bishydroperoxides: Hydrolysis with the removal of hydroperoxide groups to form a ketone

A new property of geminal bishydroperoxide was discovered: the ability to hydrolyze in acid medium in the presence of hydrogen peroxide with the formation of ketones. The most resistant to hydrolysis are the cyclic C6-bishydroperoxydes: at room temperature within one day they are practically not hydrolyzed; less stable is bishydroperoxycycloheptane (C7): in a day its one fifth part is hydrolyzed. Bishydroperoxydes with the cycles of C8 and C12 for the same time hydrolyzed to 80 and 90% respectively. Of the two linear bishydroperoxydes, 2,2-dihydroperoxydecane, with sterically unhindered center, is more resistant to hydrolysis than 6,6-dihydroperoxyundecane.

A new approach to arylaliphatic 1,5-, 1,6-, and 1,7-dicarbonyl compounds and their monoacetals based on direct anodic oxidation of 1-phenyl- and benzo[c]cycloalkenes

A new simple approach to ω-benzoylalkanals, 2-((ω-formylalkyl)benzaldehydes, and their monoacetals was developed based on direct anodic oxidation of I-phenylcycloalkenes and benzo[ccycloalkenes in methanol followed by acid hydrolysis of the electrolysis products. The target products are obtained in 53–72 % yields.

Electrochemical cleavage of a benzylic C--C bond in arylaliphatic compounds

Electrochemical cleavage of a benzylic C-C bond in arylaliphatic compounds and the effect of the structure of their alkyl and aryl fragments on the process are studied. Cleavage was found to be the most effective for substituted benzenes and anisoles with side chains bearing vicinal methoxy- and hydroxy-groups in the a- and β-positions. Cleavage was moderate for cior β-methoxy(hydroxy)- and (β,β-dialkoxyalkyl)arenes. Electrolysis carried out in methanol results in formation of PhCH2OMe and PhCH(OMe)2 from PhCH2R and PhCH(OMe)R, benzaldehyde from (1,2-dihydroxypropyl)benzene, acetophenone from 2-phenylhexan-2-ol, 4-MeOC6H4CH(OMe)2 from 4-(1,2-dimethoxypropyl)anisole, and 2-(MeO)2CHC6H4CH(OMe)2 from 1,2-dimethoxyindan.

ELECTROCHEMICAL CLEAVAGE OF THE DOUBLE BOND OF 1-ALKENYLARENES

A study has been made of the electrochemical cleavage of the double bond of propenylbenzene (Ia) and p-propenylanisole (Ib), which takes place upon anodic oxidation of (Ia, b) in alcoholic solutions of sodium trifluoroacetate and other electrolytes and which leads to conversion of (Ia, b) to benzaldehyde dialkylacetals. Conditions are found that provide for highly selective (>80%) conversion of (Ib) and p-propenyl toluene to p-methyl- and p- methoxybenzaldehyde dimethylacetals.

Peroxydisulfate-initiated reactions of 1-heptene with acetic and propionic acids

1. A study was made of the sodium peroxydisulfate-initiated reaction of 1-heptene with acetic and propionic acids at 90–105°, as well as the effect of potassium hydroxide on this reaction. 2. We were the first to discover that an olefin can be oxidized by a peroxydisulfate. The composition and character of the oxidation products are in agreement with the mechanism of a one-electron oxidation of the olefin and the formation of the cation-radical\(R--CH--\mathop {CH_2 }\limits^ + \) as the primary reaction product. 3. Potassium hydroxide substantially suppresses the oxidation of the olefin by the peroxydisulfate and facilitates the homolytic alkylation of acids by the olefin.

Electrosynthesis of esters of mono- and dioxoalkanoic and alkanedioic acids on the basis of nitro-substituted alkyl carboxylates and cycloalkanones

A one-pot electrochemical method for the synthesis of methyl monooxoalkanoates with the carbonyl group in position 4, methyl dioxoalkanoates with the oxo groups in positions 4,7-, 6,9-, 7,10-, and 12,15, and methyl 4-oxoalkanedioates was developed. This method is based on amperostatic electrolysis in an undivided cell of the salts of esters of nitroalkaniic acids and their adducts with CH2=CHX (X = Ac, CO2Me).