Metal ion initiated halogenation reactions of <i>N</i>-haloamines

Tanner, Dennis D.; Mosher, Melvyn W.

doi:10.1139/v69-117

Cited by 8 publications

(3 citation statements)

References 14 publications

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“…Nevertheless, one analogy with the present data is the fact that the major product of this, and related, free radical halogenations (5,6), is the isomer substituted at the penultimate position. Reactions of lactones with 38% hydrochloric acid In marked contrast to the facile conversion of n-alkano-yor 6-lactones into haloacids by HI or HBr, little reaction occurred under reflux in HCl (37%).…”

Section: Sources Of Variations In Haloacid Compositionsupporting

confidence: 81%

Formation of isomeric monohalo-n-alkanoic acids in the reactions of γ- and δ-n-alkanolactones with hydrogen halides

Granata¹,

Perlin²

1993

Can. J. Chem.

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ALESSANDRO GRANATA and ARTHUR S. PERLIN. Can. J. Chem. 71, 864 (1993). In 57% hydriodic acid or 48% hydrobromic acid, under reflux, n-alkanoic y-or &lactones of from 5 to 18 carbon atoms undergo facile ring opening to monohalo-n-alkanoic acids. With both reagents the ratio of acid to lactone at equilibrium varies widely, ranging from about 1 : 3 for y-valerolactone (C5) to 3 : 1 or more for y-octanolactone and the larger members of the series. Extensive scrambling of the halogen atoms accompanies the formation of the haloacids, whereby mixtures of monohalo isomers substituted at all positions from C-4 to the penultimate carbon are found. In an 18 h reaction with HBr, for example, y-caprolactone was converted into a 1 : 3 mixture of 4-and 5-bromohexanoic acids, and y-decanolactone into a 1 : 1.4: 1.4: 1.4:2.3:2.3 mixture of 4-, 5-, 6-, 7-, 8-, and 9-bromodecanoic acids. By contrast, the y-lactones containing 14 or 16 carbon atoms gave only 10: 1 mixtures of the 4-and 5-bromoacids, and at the level of 18 carbon atoms rearrangement was no longer evident; i.e., y-octadecanolactone afforded only 4-bromooctadecanoic acid. Similar isomer distributions were obtained for the iodoacid homologs. Hydrochloric acid (37%) was far less effective in opening the lactone rings, and also in inducing rearrangement of the chlorine atoms introduced. Differences in entropy and in solvation appear to be the main factors contributing to the variations observed among isomeric lactones.ALESSANDRO GRANATA et ARTHUR S. PERLIN. Can. J. Chem. 71, 864 (1993).Soumis a de l'acide iodhydrique a 57% ou a de l'acide bromhydrique 48%, les y-ou &lactones des acides n-alcanoi'ques comportant de 5 a 18 atomes de carbone donnent facilement lieu a une ouverture de cycle conduisant aux acides n-alcanoi'ques monohalogCnCs. Avec les deux rCactifs, le rapport des concentrations d'acide et de lactone prCsentes 5 l'kquilibre varie considkrablement; il passe d'environ 1 : 3 pour la y-valkrolactone (C5) a 3 : 1 ou plus pour la y-octanolactone et les autres grands cycles de la sCrie. La formation des haloacides s'accompagne de beaucoup de brouillage des halogknes; on retrouve des melanges de dCrivCs monohalogknks dans lesquels les halogknes sont fixes sur chacun des carbones de l'acide, de la position 4 jusqu'a l'avant dernier carbone. Par example, lors d'une rkaction de 18 h avec du HBr, la y-caprolactone a CtC transformfie en un mklange 1 : 3 des acides 4-et 5-bromohexanoi'ques alors que la y-dkcanolactone est transformCe en un mklange 1 : 1,4 : 1,4 : 1,4 : 2,3 : 2,3 des acides 4-, 5-, 6-, 7-, 8-et 9-bromodCcanoi'ques. Par ailleurs, les y-lactones contenant 14 ou 16 atomes de carbone ne donnent que des mklanges 10 : 1 des acides 4-ou 5-bromCs alors que, au niveau de 18 atomes de carbone, on n'observe plus de transposition, c'est-adire que la y-octadkcanolactone ne fournit que de l'acide 4-bromoctanoi'que. On a obtenu des distributions semblables avec analogues iodCs. L'acide chlorhydrique (37%) est beaucoup moins efficace pour ouvrir les cycles des lactones et ...

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Section: Sources Of Variations In Haloacid Compositionsupporting

confidence: 81%

Formation of isomeric monohalo-n-alkanoic acids in the reactions of γ- and δ-n-alkanolactones with hydrogen halides

Granata¹,

Perlin²

1993

Can. J. Chem.

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“…A reinvestigation suggested that halogenation proceeded via the chlorine atom as the chain-propagating species (eq 113). 243 The hypothesis was based on the fact that the isomer…”

Section: Arsenic and Antimony Compoundsmentioning

confidence: 99%

Chemistry of N-bromamines and N-chloramines

Kovacic¹,

Lowery²,

Field³

1970

Chem. Rev.

209

105

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“…The substructure of the modern reef is Miocene in age and probably much of the reef volume is Miocene (Tanner 1969). During the early Miocene, much of the Papuan Basin appears to have been divided into basins and shelf areas by a system of more or less continuous barrier or elongate reef zones.…”

mentioning

confidence: 99%

Evolution of the far northern barrier reefs

Veron

1978

Phil. Trans. R. Soc. Lond. B

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The basement and much of the volume of the northern barrier reefs are Miocene in age. Formation of the ancestral northern barrier reefs was greatly affected by late Miocene crustal instability associated with formation of the Papuan Basin. Present physiographic features are primarily the product of Quaternary eustatic changes. Present morphologies of the deltaic and far northern dissected reefs are discussed in relation to what is known of the geological history of the area.

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Metal ion initiated halogenation reactions of N-haloamines

Cited by 8 publications

References 14 publications

Formation of isomeric monohalo-n-alkanoic acids in the reactions of γ- and δ-n-alkanolactones with hydrogen halides

Formation of isomeric monohalo-n-alkanoic acids in the reactions of γ- and δ-n-alkanolactones with hydrogen halides

Chemistry of N-bromamines and N-chloramines

Evolution of the far northern barrier reefs

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