Synthesis of some bicyclo[2.2.2]oct-5-en-2-ones and bicyclo[2.2.2]octan-2-ones. Rearrangements accompanying oxidative decarboxylation with lead tetraacetate

1981 ◽  
Vol 59 (2) ◽  
pp. 344-355 ◽  
Author(s):  
Peter Yates ◽  
Gordon E. Langford
Keyword(s):  
Dicarboxylic Acid ◽  
Acyl Migration ◽  
Dicarboxylic Acids ◽  
Acid Group ◽  
Major Product ◽  
Lead Tetraacetate ◽  
Oxidative Decarboxylation ◽  
Similar Treatment ◽  
Carbonium Ion ◽  
A Minor

1-Methoxy-2-methyl-1,4-cyclohexadiene (3), 2-methoxy-1-methyl-1,3-cyclohexadiene (2), and 2-methoxy-1,5,5-trimethyl-1,3-cyclohexadiene (14) on heating with maleic anhydride give 1-methoxy-endo-7-methylbicyclo[2.2.2]oct-5-ene-syn-2,3-dicarboxylic acid anhydride (7) and its 6-methoxy-1-methyl (16a) and 6-methoxy-1,8,8-trimethyl (16b) analogues, respectively. On hydrolysis 16a and 16b give the corresponding keto dicarboxylic acids, 18a and 18b, via keto anhydrides 17a and 17b. Treatment of 18b with lead tetraacetate gives 1,8,8-trimethylbicyclo[2.2.2]oct-5-en-2-one (19) together with products in which rearrangement to a bicyclo[3.2.1]octane system has occurred. Treatment of 17b with bis(triphenylphosphino)nickel dicarbonyl gives only 19; similar treatment of 17a gives 1-methylbicyclo[2.2.2]oct-5-en-2-one (1). Reaction of bicyclo[2.2.2]octane-2,3-dione (27) with methyllithium gives 3-hydroxy-3-methylbicyclo[2.2.2]octan-2-one (28), its dimer 31, and a diol 30. Treatment of 5-exo-acetoxy-1, 5-endo-dimethyl-6-oxobicyclo[2.2.2]octane-anti-2,3-dicarboxylic acid (37) with lead tetraacetate gives 3-endo-acetoxy-1,3-exo-dimethyl-bicyclo[2.2.2]oct-5-en-2-one (33) as a minor product; the major product is derived by rearrangement to a bicyclo[3.2.1]octane system. It is proposed that this rearrangement, like that of 18b, involves oxidative decarboxylation of a single carboxylic acid group to give a carbonium ion that undergoes rearrangement via a 1,2-acyl migration.

Oxidative Decarboxylation of Some Bicyclo[4,1,0]hept-3-ene-1,6-dicarboxylic Acids

1979 ◽  
Vol 32 (8) ◽  
pp. 1743 ◽  
Author(s):  
N Galloway ◽  
B Halton
Keyword(s):  
Dicarboxylic Acids ◽  
Lead Tetraacetate ◽  
Oxidative Decarboxylation ◽  
Acid Anhydrides

Treatment of the bicyclo[4,1,0]hept-3-ene-1,6-dicarboxylic acids (6d-f) with lead tetraacetate under a variety of conditions results in oxidative decarboxylation and formation of the isobenzofuranl(3H)-ones (9a-c) and (10c). In addition, the corresponding acid anhydrides (7a-c) are formed and these are resistant to oxidative decarboxylation.

The mechanism of lead tetraacetate decarboxylation. II. 2,3,3-Trimethylbutanoic and Adamantane-2-carboxylic acids

1974 ◽  
Vol 27 (8) ◽  
pp. 1693 ◽  
Author(s):  
ALJ Beckwith ◽  
RT Cross ◽  
GE Gream
Keyword(s):  
Acetic Acid ◽  
Carboxylic Acid ◽  
Carboxylic Acids ◽  
Major Product ◽  
Lead Tetraacetate ◽  
Oxidative Decarboxylation ◽  
Catalysed Reaction

Oxidative decarboxylation of 2,3,3-trimethylbutanoic acid with lead tetraacetate in benzene or acetic acid affords mainly 3,3-dimethylbut-2-yl acetate; the major product from the cupric salt catalysed reaction is 3,3-dimethylbut-1-ene. The low yields detected of rearrangement products provide evidence for the intermediacy of organolead and organocopper compounds which decompose by SNi displacement or cyclic cis-elimination. Other reactions discussed are oxidative decarboxylation of adamantane-2-carboxylic acid, deamination of 3,3-dimethylbut-2-ylamine, and thermolysis of bis(2,3,3-trimethylbutanoyl) peroxide and of t-butyl adamantane-2-percarboxylate. A reinterpretation of previous results on the oxidative decarboxylation of exo- and endo-nor- bornane-2-carboxylic acid with lead tetraacetate is presented.

REACTIONS OF OZONIDES: III. OZONOLYSIS OF ETHYL 10-UNDECENOATE IN ETHANOL

1965 ◽  
Vol 43 (2) ◽  
pp. 319-327 ◽  
Author(s):  
D. G. M. Diaper ◽  
D. L. Mitchell
Keyword(s):  
Sebacic Acid ◽  
Major Product ◽  
Alkyl Ester ◽  
Similar Treatment ◽  
Oxidative Esterification ◽  
Temperature Range ◽  
Ester Formation ◽  
Minor Degree ◽  
A Minor ◽  
Undecenoic Acid

Diethyl sebacate was the major product obtained by ethanolysis of the ozonization products of ethyl 10-undecenoate in the temperature range 28 to 170 °C. Mixed esters of sebacic acid were similarly obtained, in poor to moderate yields, by alcoholysis of the ozonization product from an alkyl ester of 10-undecenoic acid in the appropriate alcohol. Sebacic acid half esters are prepared by a similar treatment of the ozonization products from 10-undecenoic acid itself. Ester formation has been shown to proceed mainly by rearrangement of an alkoxyhydroperoxide, with oxidative esterification of an aldehyde intermediate contributing to a minor degree.

IR and 13C, 17O, and 119Sn NMR spectra of some bis(1-butyl)tin(IV) carboxylates of dicarboxylic acids

1991 ◽  
Vol 56 (9) ◽  
pp. 1908-1915 ◽  
Author(s):  
Jaroslav Holeček ◽  
Antonín Lyčka ◽  
Milan Nádvorník ◽  
Karel Handlíř
Keyword(s):  
Infrared Spectroscopy ◽  
Nmr Spectroscopy ◽  
Dicarboxylic Acid ◽  
Nmr Spectra ◽  
Dicarboxylic Acids ◽  
119Sn Nmr ◽  
Carboxylic Groups ◽  
Cyclic Oligomers ◽  
The Media ◽  
Oxygen Atoms

Infrared spectroscopy and multinuclear (13C, 17O, and 119Sn NMR spectroscopy have been used to study the structure of bis(1-butyl)tin(IV) carboxylates of dicarboxylic acids (1-C4H9)2. Sn(X(COO)2), where X = (CH2)n (n = 0-8), CH=CH (cis and trans) and C6H4 (ortho and para).The crystalline compounds are formed by linear or cyclic oligomers or polymers whose basic building units represent a grouping composed of the central tin atom substituted by two 1-butyl groups and coordinated with both oxygen atoms of two anisobidentate carboxylic groups derived from different molecules of a dicarboxylic acid. The environment of the tin atom has a shape of a trapezoidal bipyramid. When dissolvet in non-coordinating solvents, the compounds retain the oligomeric character with unchanged structure of environment of the central tin atom. In the media of coordinating solvents the bis(1-butyl)tin(IV) carboxylates of dicarboxylic acids form complexes whose central hexacoordinated tin atom binds two molecules of the solvent trough their donor atoms. Carboxylic groups form monodenate linkages in these complexes.

Nucleophilic addition at u 3 -alkyne clusters leading to carbon-carbon bond formation

1982 ◽  
Vol 308 (1501) ◽  
pp. 59-66 ◽  
Keyword(s):  
Bond Formation ◽  
Organic Ligand ◽  
Major Product ◽  
Unsaturated Hydrocarbon ◽  
Terminal Alkynes ◽  
Hydrogen Atoms ◽  
Metal Atoms ◽  
Carbon Carbon Bond ◽  
Anionic Species ◽  
A Minor

Reactions of nucleophiles with triosmium carbonyl clusters, especially those containing unsaturated hydrocarbon ligands, are discussed. Attack may be at CO, the metal atoms, at carbon of the organic ligand, or, where there are acidic metal-bound hydrogen atoms, deprotonation to give anionic clusters may occur. New results on the reactions of LiBHEt3 with p3-alkyne clusters of type Os3(CO)10 (RC2R') are considered in the light of the range of possible sites of attack. Protonation of anionic species that are formed gives hydrogenation products with or without the loss of CO. Os3H2(CO)9(RC2R') is usually a minor product, while C-C coupling leads to Os3H(CO)9(CRCR'COH) (in general the major product) and to Os3H(CO)9- (CRCR'CH). With terminal alkynes RC2H H-atom transfer accompanies C-C coupling to give Os3H(CO)9(RC—C =C H 2) in substantial amounts. The initial site of hydride attack (CO, alkyne or metal) is considered in the context of low-temperature 1H n.m.r. results.

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