The ELECTROLYSIS OF Ω-Bromocarboxylic ACIDS

Woolford, R. G.

doi:10.1139/v62-280

Cited by 24 publications

(12 citation statements)

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“…The 2,2,13,13-tetraphenyltetradecanedioic acid The lactone analogue of 4d (29) was synthesized by replacing one CH3 at position 3 and one at position 13 of 4d with CH2OH functions. One equivalent of 1,1-diiododecane was condensed with 2 equiv of a-methylbutyrolacone (25) (eq 4), and the resulting bis(a-lactone) 26 was converted into the bis(/3-lactone) of 3,14-bis(hy-( 16) E.g., (a) Lerman, O.; Rozen, S. J. Org.…”

Section: Resultsmentioning

confidence: 99%

Synthesis and hypolipidemic and antidiabetogenic activities of .beta.,.beta.,.beta.',.beta.'-tetrasubstituted, long-chain dioic acids

Bar‐Tana¹,

S²,

Jc³

et al. 1989

J. Med. Chem.

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beta,beta,beta',beta'-Tetrasubstituted, long-chain dioic acids of the general formula HOOC-C(XY)-C(R2)-Q-C-(R2)-C(XY)-COOH have been synthesized and evaluated as hypotriglyceridemic-hypocholesterolemic agents in rats and as antidiabetogenic agents in ob/ob diabetic mice. The free carboxyl function of analogues of the series was mandatory for their hypolipidemic-antidiabetogenic effect while nonhydrolyzable diesters were inactive. Other structure-activity relationships were determined as a function of the overall chain length (C12-C22), alpha,alpha'-substitutions (X, Y = H, F, Cl, Br, OH, CN), beta, beta'-substitutions (R = CH3, C6H5), and core substitutions [Q = (CH2)10, (CH2)4CH = CH(CH2)4, 1,4-C6H10[(CH2)3]2, 1,4-C6H4[(CH2)3]2, 1,4-C6H4(CH = CHCH2)2, CH2(OCH2CH2)3OCH2)]. The most effective hypolipidemic-antidiabetogenic members of the series were alpha,alpha'-nonsubstituted, beta,beta'-methyl-substituted analogues of 14-18-carbon chains having either a saturated aliphatic core or a 1,4-bis(propenyl)benzene core in the cis/trans configuration. The hypotriglyceridemic rather than the hypocholesterolemic capacity of members of the series was found to correlate with their respective capacities as liver peroxisomal proliferators in rats.

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Section: Resultsmentioning

confidence: 99%

Synthesis and hypolipidemic and antidiabetogenic activities of .beta.,.beta.,.beta.',.beta.'-tetrasubstituted, long-chain dioic acids

Bar‐Tana¹,

S²,

Jc³

et al. 1989

J. Med. Chem.

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“…Me 3 N + (CH 2 ) 12 NMe 3 + and Me 3 N + (CH 2 ) 14 NMe 3 + were obtained from 1,12-dibromododecane (commercially available) and 1,14-dibromotetradecane as described in the literature . 1,14-Dibromotetradecane was prepared by Kolbe’s electrolysis of the α-bromo carboxylic acid in methanol . Me 3 N + (CH 2 ) 10 NMe 3 + (commercially available, Sigma-Aldrich).…”

Section: Methodsmentioning

confidence: 99%

“…52 1,14-Dibromotetradecane was prepared by Kolbe's electrolysis of the α-bromo carboxylic acid in methanol. 53 STD spectra were acquired on a Varian Inova 17.6 T spectrometer (750 MHz proton resonance) equipped with an inverse-detection triple-resonance probe 1 H/ 13 C/ 31 P and triple-axis-shielded PFGs for use with conventional 5 mm NMR tubes. The spectra were obtained at a temperature of 25°C, and the chemical shifts reported are referenced to the lock deuterium solvent.…”

Section: ■ Conclusionmentioning

confidence: 99%

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Kinetic Study of [2]Pseudorotaxane Formation with an Asymmetrical Thread

et al. 2016

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Kinetic and thermodynamic studies on cyclodextrin (CD)-based [2]pseudorotaxane formation have been carried out by a combination of NMR and calorimetric techniques using bolaform surfactants as axles. Experimental evidence of the formation of an external complex between the trimethylammonium head groups of the axle and the external hydrogen atoms of α-cyclodextrin (α-CD) is reported. Inclusion of this external complex in the reaction pathway allows us to explain the kinetic behavior as well as the nonlinear dependence of the observed rate constant on CD concentrations. The equilibrium constant for [2]pseudorotaxane formation is strongly affected by the spacer length of the axle. This effect is a consequence of increasing rotaxane stability because the threading rate constant is almost independent of the spacer length, but dethreading strongly decreases on increasing the axle size. Using a nonsymmetrical axle with tripropyl and trimethylammonium cations precludes CD threading by the large head side. CDs will thread this asymmetrical bolaform by both their wide and narrow sides, yielding two isomeric [2]pseudorotaxanes. Threading by the wide side of the CD is 60% more favorable than that by the narrow one, but dethreading rate constants are the same for both isomers.

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“…General iMetltod of Electrolysis T h e cell used was fully described previously (6). For personal use only.…”

Section: Electrolysis Of O-ilalogenophenyl-szibstituted Acidsmentioning

confidence: 99%

THE ELECTROLYSIS OF o-HALOGENOPHENYL-SUBSTITUTED ACIDS

Woolford¹,

Lin²

1966

Can. J. Chem.

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The synthesis and electrolysis of a series of o-chloro-and o-bromo-phenyl-substituted acids with two to five carbon chain lengths have been studied. The main products, under the experimental coilditions used, were the Icolbe dimers. A complete isolation and identification of all of the important by-products is recorded. Methanol and methanol-pyridine were the solvents for electrolysis.This work represents the first study of the behavior of aromatic halogen substituents during the Icolbe electrolysis. In contrast to many reactions involving aliphatic halogen substituents, no free halogen was produced and no products were obtained, even in trace amounts, where halogen had been lost from the aromatic nucleus. During this investigation, 18 previously unreported compounds were synthesized and their properties were determined.Recently, there has been an increase in interest in the electrolysis reactions of aryIsubstituted aliphatic acids (refs. 1-4 and articles cited therein). In part, this interest has involved efforts to observe other than normal Icolbe coupling reactions, and in particular to study phenyl migration in free radicals and hoinolytic cyclization of the radicals involved. No studies \\.ere undertake11 xvith halogeilated aromatic rings. Past worl; (5, 6) has sho\\.n that halogen is readily lost during electrolysis of sollle a-halogenated aliphatic acids. I t \\as expected that halogen ivould be inore stable and thus less easily lost from an aromatic ring than from an aliphatic chain. I-Iouever, because of the coinplete laclc of work in this area, it \\.as felt 1 1 orthy of investigation. As a start, efforts \\.ere concentrated on o-chloro-and o-broino-phenyl-substituted acids of two to five carbon chain lengths. I t was hoped to learil something of the radicals produced, their reactions, and to \\hat extent this class of organic acids might be used in the synthesis of IrI broluide and chloride 1 1 it11 sodium cyanide; hydrolysis gave the desired acids. This method \I a s used to prepare the necessary substituted acetic acids and extended to produce the I~alogenopl~enylb~~tai~oic acids.

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The ELECTROLYSIS OF Ω-Bromocarboxylic ACIDS

Cited by 24 publications

References 0 publications

Synthesis and hypolipidemic and antidiabetogenic activities of .beta.,.beta.,.beta.',.beta.'-tetrasubstituted, long-chain dioic acids

Synthesis and hypolipidemic and antidiabetogenic activities of .beta.,.beta.,.beta.',.beta.'-tetrasubstituted, long-chain dioic acids

Kinetic Study of [2]Pseudorotaxane Formation with an Asymmetrical Thread

THE ELECTROLYSIS OF o-HALOGENOPHENYL-SUBSTITUTED ACIDS

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