Novel type of rearrangement of the carane system into a 2-methyl-4-isopropylbicyclo[3.1.0]hexane skeleton

Conclusions X-ray structural analysis has established that one of the oxidation products of 3-carene by trivalent thallium acetate is 2-methyl-4-(1-hydroxy-1-methylethyl)bicyclo [3.1.0]-hexan-2-ol. Its formation depends primarily on rearrangement of the carane skeleton into a bicyclohexane skeleton via 1,3-trans-annular participation of the C⁶-C⁷ bond in the cyclopropane fragment.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 8, pp. 1777–1779, August, 1988.     

Oxidation of 3-carene with Pb(OAc)4 in benzene

Conclusions The products of the oxidation of 3-carene with lead tetraacetate in benzene contain, besides the previously identified compounds, also the acetates of trans-4-caren-3-ol, m-mentha-1,3-dien-8-ol and 2-(m-tolyl)-2-propanol, which serves to confirm the assumption that the given reaction proceeds in two directions: a) with the formation of the allylic organolead derivative; and b) of the adduct of 3-carene with Pb(OAc)₄, as intermediate products.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 1, pp. 45–49, January, 1973.     

Kinetics and mechanism of Ru(III) catalysed oxidation of some polyhydric alcohols by N-bromosuccinimide in acidic media

Kinetics of oxidation of ethylene glycol, glycerol, erythritol and dulcitol by acidic solution of N-bromosuccinimide (NBS) in presence of ruthenium(III) chloride as a homogeneous catalyst and mercuric acetate as scavenger in the temperature range of 30–50°C have been reported. The reactions follow identical kinetics, being first order in each NBS, substate and Ru(III). Zero effect of [H⁺], [mercuric acetate] and ionic strength has been observed. A negative effect of succinimide and acetic acid is observed while [Cl^-] shows the positive effect on reaction velocity. Various activation parameters have been computed. The products of the reaction were identified as the coresponding acids. A suitable mechanism consistent with the experimental results has been proposed.     

Synthesis of 5-Formyl and 5-Acyl-1,2-dithiole-3-ones

The preparation of new 5-formyl-, 5-acetyl- and 5-propionyl-1,2-dithiole-3-ones by oxidation of the corresponding 1,2-dithiole-3-thiones with mercuric acetate is described.     

Menthatrienes and the Oxidation of Limonene

The oxidation of limonene with mercuric acetate gives a mixture containing mentha-1. 3. 8-triene, the hydrocarbon of parsley, and its isomer, mentha-1. 4. 8-triene. Selenium dioxide oxidation of limonene in alcohol gives as the main product mentha-1. 8-dien-4-ol, and pyrolysis of the acetate of the latter, or of mentha-1. 8-dien-10-yl acetate (the main product of the oxidation of limonene with selenium dioxide in acetic anhydride), also gives a mixture of menthatrienes. A discussion of the selenium dioxide oxidation of limonene is presented.     

Cyclization of dienols, polyenes, and dienyne mediated by mercuric salts: course of cyclizations controlled by stability of cationic intermediates

Course of cyclization of dienols, polyenes, and dienyne mediated by mercuric salts were controlled by stability of cationic intermediates and source of mercuric salts. Reaction of (E)-5,9-dimethyl-4,8-decadiene-1-ol with mercuric acetate gave the intramolecular oxymercuration product, whereas one with mercuric triflate produced the olefin cyclization products.     

Cyclization of 3-Cyclopent-2-Enyl-4-Hydroxy[1]Benzopyran-2-One

Cyclization of 3-cyclopent-2-enyl-4-hydroxy[1]benzopyran-2-one (1) with cold cone. sulfuric acid gave a mixture of two products, 2 (10%) and 3 (80%). However, on treatment with mercuric chloride 1 furnished the linear product 4 in 60% yield while with mercuric acetate the bicyclic product 8 was obtained in 50% yield. The structures of products are established by chemical correlation.     

Cyclopalladated imines in synthesis: the preparation of unsymmetrical stilbenes and 3-arylisoquinolones

A series of cyclopalladated t-butylimines of aromatic aldehydes were reacted with styrene to give o-formylstilbenes in high yield. The $\text{N}$-methylimines of these were converted to 3-aryl-$\text{N}$-methyl-isoquinolones by oxidation with mercuric acetate.     

A new route to heterocyclic compounds by the mercuric acetate oxidation of N-alkyl substituted 4-piperidones

N-Alkyl substituted 4-piperidones readily undergo oxidation in high yield upon reaction with mercuric acetate. Application of the oxidation to the synthesis of the skeletal framework of several alkaloids is described.     

Mechanism of oxidation of some aliphatic ketones by N-bromosuccinimide in acidic media

Kinetics of the oxidation of methyl n-propyl ketone and methyl isobutyl ketone by N-bromosuccinimide (NBS) have been studied in perchloric acid media in presence of mercuric acetate. A zero order dependence to N-bromosuccinimide and a first order dependence to both ketones and hydrogen ion concentrations have been observed. Sodium perchlorate, mercuric acetate and succinimide additions have negligible effect while methanol addition has a positive effect on the reaction rate. A solvent isotope effect (k₀D₂O/K₀H₂O = 2.3-2.7 and 2.4-2.8 for MeCOn.pr and MeCoi-Bu, respectively) has been observed at 35°. Kinetic investigations have revealed that the order of reactivity is methyl n-propyl ketone > methyl isobutyl ketone. Various thermodynamic parameters have been computed and corresponding 1,2-diketones were found to be the products. A suitable mechanism in conformity with the above observations has been proposed.     

Secondary tritium isotope effects,a useful mechanistic probe for the study of acetoxyl participation and transfer

Tritium labelling on the acetoxyl methyl group has been used to probe the mode of incorporation of acetate into cinnamyl acetate in the solvolyes of cinnamyl chloride and cinnamylmercuric acetate, and in the allylic oxidation of allylbenzene with mercuric acetate.     

Synthese von derivaten der cinchona-alkaloide—XXXII Synthese von dihydrocorynanthean und 3-epidihydrocorynanthean aus cinchonin

Starting from cinchonine, 3-epidihydrocorynantheane was synthesized through 2′-oxohexahydrocinchonine. Quinine was transformed into 10-methoxydihydrocorynantheane by the same reaction steps. In both cases, it was found that Oppenauer oxidation of the secondary hydroxyl group at quinine-numbering C-9 was accompanied with no configurational change at the neighboring C-atom, which originated from C-8 in quinuclidine moiety. 3-Epidihydrocorynantheane was converted to dihydrocorynantheane by oxidation with mercuric acetate and then sodium borohydride reduction.     

Synthesis of new chiral schiff bases from (+)-3-carene and their use in asymmetric oxidation of sulfides catalyzed by metal complexes

A number of new chiral Schiff bases were synthesized starting from accessible monoterpene (+)-3-carene, and the products were used as ligands in metal complex-catalyzed oxidation of sulfides to chiral sulfoxides. The optical purity and the sign of optical rotation of chiral sulfoxides were found to strongly depend on the oxidation temperature.     

Synthesis of new chiral 2,2'-bipyridine ligands and their application in copper-catalyzed asymmetric allylic oxidation and cyclopropanation

A series of modular bipyridine-type ligands 1 and 3-9 has been synthesized via a de novo construction of the pyridine nucleus. The chiral moieties of these ligands originate from the isoprenoid chiral pool, namely, beta-pinene (10 --> 1), 3-carene (14 --> 3 and 5), 2-carene (28 --> 4), alpha-pinene (43 --> 6-8), and dehydropregnenolone acetate (48 --> 9), respectively. Copper(I) complexes, derived from these ligands and (TfO)(2)Cu (1 mol %) upon an in situ reduction with phenylhydrazine, exhibit good enantioselectivity (up to 82% ee) and unusually high reaction rate (typicaly 30 min at room temperature) in allylic oxidation of cyclic olefins (52 --> 53). Copper-catalyzed cyclopropanation proceeded with < or =76% enantioselectivity and approximately 3:1 to 99:1 trans/cis-diastereoselectivity (54 --> 55 + 56). The level of the asymmetric induction is discussed in terms of the ligand architecture that controls the stereochemical environment of the coordinated metal.     

Kinetics and mechanism of oxidation of cyclopentanone by N-bromosuccinimide

N-bromosuccinimide oxidation of cyclopentanone in acidic media in presence of mercuric acetate has been made. A zero order dependance to N-bromosuccinimide and a first order dependence to cyclopentanone and hydrogen ion concentration has been observed. Ionic strength, mercuric acetate and succinimide has negligible effect while methanol addition has a positive effect. Various rate parameters have been computed and 1,2-cyclopentanedione identified as the end product. A suitable mechanism in confirmity with the above observations has been proposed.With 2 Figures     

Routes To trans-Chrysanthemic Acid,IV1 Synthesis from 4-Acetyl-2-Carene

4-Acetyl-2-carene obtained from 3-carene undergoes methylation, ozonolysis, and lead tetraacetate oxidation resulting in cis-dihydrochrysanthemolactone.     

Kinetics and mechanism of oxidation of secondary alcohols by potassium bromate

The oxidation by Br(V) of propan-2-ol follows the rate law (?d[Br(V)]/dt) = k₄ [alcohol][Br(V)][H⁺]². The initial reaction is complicated by the presence of the product bromide ion. The reaction is composed of two second order reactions—the first, a comparatively slow one and the second stage, a faster reaction which is mainly bromine oxidation. The pure bromate oxidation can be followed by the initial addition of mercuric acetate which prevents the accumulation of bromine in the system under these conditions. The reaction rate does not depend on the nature and structure of the alcohol. A mechanism involving a slow rate-determining formation of an alkyl-bromate ester followed by a fast decomposition to the products is in accord with the observed results.     

Syntheses and properties of photochromic polymers of the mercury thiocarbazonate series

Photochromic vinyl polymers of the mercuric thiocarbazonate series were synthesized via the three sequences: (1) synthesis of p-(meth)acrylamidophenyl mercuric acetate(II) by the reaction of (meth)acrylyl chloride with p-aminophenyl mercuric acetate, followed by polymerization to afford corresponding polymers(III) and subsequent reaction with diphenyl- or di-β-naphthyl-thiocarbazone, (2) alternative preparation of III by the reaction of (meth)acrylyl chloride polymers with p-aminophenyl mercuric acetate, and (3) reaction of N-hydroxymethyl (meth)acrylamide polymers with p-amidophenyl mercuric thiocarbazonates. The photochromic behavior of these polymers was investigated to provide data which might indicate the effect of steric conditions on the isomerization of the photochromic components in polymers both under illumination and in dark recovery.     

2-Carene in the Prins reaction

The Prins reaction of 2-carene with formaldehyde has been studied. The main reaction product is 2-hydroxymethyl-3-carene. The dehydration of 2-hydroxy-methyl-3-carene is accompanied by a skeletal rearrangement of the carane structure with the formation of products having a seven-membered ring.Institute of Physical Organic Chemistry, Belorussian SSR Academy of Sciences, Minsk. Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 193–198, March–April, 1989.     

Products of the catalytic liquid-phase oxidation of 3-carene

The liquid-phase oxidation of 3-carene in the presence of various catalytic systems has been studied. The possibility has been shown of the directed preparation of 3-carene oxide, of ketones with a carane skeleton and a 7-membered ring, or of aromatic tertiary alcohols.Institute of Physical Organic Chemistry, Academy of Sciences of the Belorussian SSR, Minsk. Translated from Khimiya Prirodnykh Soedinenii, No. 3, pp. 328–334, May–June, 1991.