Mechanism of carbon-halogen bond cleavage. III. Electrochemical preparation of highly strained hydrocarbons

Rifi, M. R.

doi:10.1135/cccc19710932

Cited by 32 publications

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“…There have been numerous and extensive investigations of the electrochemistry of ␣,-dihaloalkanes, owing to their importance as starting materials for the synthesis of a variety of other organic compounds. For example, both direct and mediated electrochemical reductions of 1,3-dihalopropanes at mercury, aluminum, carbon, and platinum cathodes afford cyclopropane as a major product, [1][2][3][4][5][6][7][8][9] which could be formed from either a radical or carbanion intermediate. By comparing product distributions for the direct electrochemical reductions of meso-and dl-2,4-dibromopentane in dimethyl sulfoxide containing tetraethylammonium bromide, Fry and Britton 10,11 established that cyclopropane arises via a pathway involving intramolecular cyclization of an electrogenerated halocarbanion intermediate, because cis-and trans-1,2-dimethylpropane were obtained equally from electrolyses of the two diastereomers.…”

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confidence: 99%

Catalytic Reduction of 1,6-Dihalohexanes by Nickel(I) Salen Electrogenerated at Glassy Carbon Cathodes in Dimethylformamide

Vanalabhpatana

Peters

2005

J. Electrochem. Soc.

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Reaction between stoichiometric amounts of 1,6-dihalohexanes and electrogenerated nickel͑I͒ salen in dimethylformamide containing 0.10 M tetramethylammonium tetrafluoroborate affords cyclohexane in up to 78% yield. Arising via a radical pathway, an -haloalkylnickel͑II͒ species is a proposed intermediate for these reductions in which alkanes, 1-alkenes, and aldehydes are also produced. In cyclic voltammetric studies at scan rates of 5-25 mV s −1 , formation of a passivating film on the surface of the carbon cathode has a dramatic effect on the catalytic reduction of 1,6-dihalohexanes, but this electrode fouling can be overcome by addition of acetic acid to the medium. For controlled-potential electrolyses involving the reduction of a 1,6-dihalohexane with catalytic amounts of electrogenerated nickel͑I͒ salen in the presence of excess acetic acid, most of the substrate is converted into three different esters ͑hexyl acetate, 1,6-diacetoxyhexane, and dodecyl acetate͒ which arise via nucleophilic ͑S N 2͒ attack of acetate ion on the dihaloalkane.

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confidence: 99%

Catalytic Reduction of 1,6-Dihalohexanes by Nickel(I) Salen Electrogenerated at Glassy Carbon Cathodes in Dimethylformamide

Vanalabhpatana

Peters

2005

J. Electrochem. Soc.

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“…The 31P and 13C NMR parameters for a series of jV-trimethylsilyltrialkylphosphinimines has recently been reported7 and Hückel -type calculations have been published with regard to the uv properties of phosphinimines and phosphazines. 8 NMR Results. The 31P, 13C chemical shifts and 13C-31P couplings are given in Tables I-III, respectively.…”

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confidence: 99%

Displacement of an alkyl group from quaternary ammonium chlorides by certain neutral nucleophiles

Lane¹,

Speier²

1976

J. Org. Chem.

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Lane and SpeierLithium in Ammonia Reduction of 1-Bromonorbornane with Inverse Addition. A solution of 134.8 mg (19.5 mmol) of lithium metal in 60 ml of twice-distilled ammonia3I was added dropwise to a rapidly stirred solution of 351.1 mg (2.00 mmol) of 1-bromonorbornane in 50 ml of doubly-distilled ammonia and 10 ml of dry diethyl ether. The characteristic blue color of lithium in ammonia was immediately discharged upon addition to the halide solution. Following the addition, excess lithium was destroyed with solid ammonium chloride as described above. GLC analysis of the ethereal residue revealed 90.6% norbornane and 9.4% 1,l'-binorbornane.Lithium in Ammonia Reduction of 1-Bromonorbornane at High Dilution. A solution of 500 mg (2.86 mmol) of 1-bromonorbornane in 50 ml of dry diethyl ether was diluted with 150 ml of twice-distilled ammonia31 and added dropwise to a rapidly stirred solution of 250 ml(35.7 mmol) of lithium in a mixture consisting of 500 ml of twice-distilled ammonia3I and 100 ml of dry diethyl ether at reflux. Following the addition, the reaction mixture was allowed to stir for 1 h a t reflux and was then quenched with solid ammonium chloride as described above. GLC analysis of the ethereal residue revealed 99.2% norbornane and 0.8% 1,l'-binorbornane.Registry No.--4, 59219-48-6; ciscyclopentane-1,3-dicarboxylic acid, 876-05-1; cis-cyclopentane-1,3-dicarboxylic acid chloride, 59219-49-7; cis-cyclopentane-l,3-bis(N,N-dimethylcarboxamide), 59219-50-0; trans-cyclopentane-l,3-bis(N,N-dimethylcarboxamide), 59219-51-1; 1,3-bis(dimethylamino)cyclopentane, 59219-52-2; Nmethyl-N-(1-norbornylmethyl)formamide, 59219-53-3; lithium, 7439-93-2; ammonia, 7664-41-7.

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“…While 1,2-dihalides generally afford olefins upon electroreduction, small-ring compounds such as cyclopropane and cyclobutane derivatives can be obtained from the corresponding 1,3-and 1,4-dihalides, respectively. 103,104 Highly strained bicyclobutanes were obtained from dihalogenated cyclobutanes. The example of Scheme 34 illustrates the synthesis of spiropentane 67 from the electrolysis of 1,3-dibromo-2,2-bis (bromomethyl)propane 66 at a mercury cathode.…”

Section: Electroreduction Involving Di-and Trihalidesmentioning

confidence: 99%

Intramolecular reductive cyclisations using electrochemistry: development of environmentally friendly synthetic methodologies

2006

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Mechanism of carbon-halogen bond cleavage. III. Electrochemical preparation of highly strained hydrocarbons

Cited by 32 publications

References 0 publications

Catalytic Reduction of 1,6-Dihalohexanes by Nickel(I) Salen Electrogenerated at Glassy Carbon Cathodes in Dimethylformamide

Catalytic Reduction of 1,6-Dihalohexanes by Nickel(I) Salen Electrogenerated at Glassy Carbon Cathodes in Dimethylformamide

Displacement of an alkyl group from quaternary ammonium chlorides by certain neutral nucleophiles

Intramolecular reductive cyclisations using electrochemistry: development of environmentally friendly synthetic methodologies

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