Bridged Ring Compounds. XIII.<sup>1-3</sup> The Reaction of N,N-Dibromobenzenesulfonamide with Bicyclo[2 2.1]heptene, Bicyclo[2.2.2]octene, and endo-Bicyclo[2.2.1]-5-heptene-2,3-dicarboxylic Anhydride

Oehlschlager, A. C.; Kennedy, C. D.; Zalkow, Leon H.

doi:10.1021/jo01344a004

Cited by 14 publications

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“…It must be emphasised that despite the compounds having been known for some decades (except the endo iodo derivative and both isomers of methylthio and methylseleno derivatives) the papers on these compounds [17][18][19][20][21][22] do not include the corresponding 1 H-NMR data. In several instances only the chemical shift for the H-3 proton is given, 20,21,23 or for groups of protons as unresolved multiplets. 22,24,25 THEORY As the theory has been given previously 1b,11,16 only a brief summary of the latest version (CHARGE8c) will be given here.…”

Section: Introductionmentioning

confidence: 99%

¹H chemical shifts in NMR. Part 24—proton chemical shifts in some gem‐difunctional compounds: 3‐endo‐ and 3‐exo‐substituted norbornanones

Gauze

Basso

Campos

et al. 2006

J of Physical Organic Chem

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The complete assignment of the 1 H and 13 C NMR chemical shifts, from 2D techniques and spectra recorded at 500 MHz, for 3-substituted norbornanones with Cl, Br, I, SMe and SeMe substituents at endo and exo positions and 3-exo-hydroxynorbornanone is reported. The observed 1 H chemical shifts are compared with the corresponding calculated values using the semi-empirical CHARGE method and ab initio calculations at the B3LYP/ 6-311þþG(d,p) theory level. The molecular geometries were obtained through Density Functional Theory (DFT) methods. Good agreement between the experimental and both sets of calculated values is observed with the CHARGE calculations being more accurate for this series. This illustrates the utility of the CHARGE program for chemical shift assignments and also as a tool for the elucidation of chemical structures. a In CDCl 3 as solvent. Signal multiplicities are indicated as singlet (s), doublet (d), double doublet (dd) and multiplet (m).

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Section: Introductionmentioning

confidence: 99%

¹H chemical shifts in NMR. Part 24—proton chemical shifts in some gem‐difunctional compounds: 3‐endo‐ and 3‐exo‐substituted norbornanones

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Campos

et al. 2006

J of Physical Organic Chem

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“…Reaction of nortricyclyl bromide (lc) in CH3COOD, 0.1 M D2S04 at 75" for 70 h gives anti-7-bromo-exo-2-norbornyl acetate-dl (4973, syn-7-bromo-exo-2-norbornyl acetate-dl (26%), exo-5-bromo-exo-2-norbornyl acetate-d, (1 Ox), endo-5-bromo-exo-2-norbornyl acetate-dl (873, 3% of unidentified mate~-ial,~-~ and 4% un-,The syn-and anti-bromoacetates, obtained from a nondeuterated-run, were identified by spectral comparison and by the melting points of the 2,4-dinitrophenylhydrazones of the corresponding bromoketones (7,8). The syn-and antichloroacetates were identified by comparison of spectral data to those of authentic samples prepared via addition of HOCl to norbornene (9) followed by acetylation.…”

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confidence: 99%

Acid-catalyzed Ring Opening of Halo-nortricyclanes

Cappelli¹,

Timmins²

1972

Can. J. Chem.

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The acid-catalyzed (CH,COOH-0.1 M H,S04) opening of the cyclopropyl ring in nortricyclyl chloride and nortricyclyl bromide gives in each case the anti-7-, syn-7-, exo-5-, and endo-5-halo-exo-2-norbornyl acetates as the major products. When the reactions are carried out in deuterated medium the deuterium is situated endo at C-6 in the anti-and syn-7-haloacetates and establishes that at least 75% of the products arise from inltzal edge protonation of the cyclopropane.L'ouverture acido catalysee (CH,COOH -0.1 M H,S04) du cycle cyclopropyle dans le chlorure et bromure de nortricyclyle, donne dans chaque cas comme produits majeurs les acetates d'anti-7, syn-7, exo-5, et endo-5-halo exo-2-norbornyl. Quand les reactions sont faites en milieu deuttrie, le deuterium est situe en endo sur le C-6 dans les 7-haloadtates anti et syn et montre ainsi que 75% au moins de produits proviennent d'une protonation initiale sur le site cyclopropane.Canadian Journal of Chemistry, 50,2163Chemistry, 50, (1972 The chemistry of protonated cyclopropane has commanded much interest. Electrophilic ' cleavage of a strained cyclopropane o bond by i the reagents DOAc-D,S04, DCl, DBr, and 1 Br, (2-6) has been studied extensively to determine the site of attack of the electrophile and : the stereochemistry of the addition of the electrophile and nucleophile. The nature of the products and the stereochemical information obtained from the D'X-additions were then used to establish the nature of the first formed intermediate resulting either from initial edge or corner protonation. Results from studies on the nortricyclane systems l a (1) and b (2) have been interpreted in terms of corner-protonated nortricyclane intermediates but did not establish whether initial protonation occurred cornerwise or edge-wise.Our interest in the preparation of the 7-haloexo-2-norbornyl brosylates-6-dl for y-deuterium isotope effect studies has led us to a study of the electrophilic cleavage (HOAc-H2S04; DOAc-D2S04) of the cyclopropane ring in 3-bromoand 3-chloro-nortricyclane (lc and d). We report results which establish that (a) the o I bond farthest removed from the electron-withdrawing halogen is cleaved preferentially via initial edge protonation, (b) the ring opening occurs with retention and inversion at the carbon atoms bearing the electrophile and nucleophile, respectively, and (c) the pathways of product formation are as described in Scheme 1.Reaction of nortricyclyl bromide (lc) in CH3COOD, 0.1 M D2S04 at 75" for 70 h gives anti-7-bromo-exo-2-norbornyl acetate-dl (4973, syn-7-bromo-exo-2-norbornyl acetate-dl (26%), exo-5-bromo-exo-2-norbornyl acetate-d, (1 Ox), endo-5-bromo-exo-2-norbornyl acetate-dl (873, 3% of unidentified mate~-ial,~-~ and 4% un-,The syn-and anti-bromoacetates, obtained from a nondeuterated-run, were identified by spectral comparison and by the melting points of the 2,4-dinitrophenylhydrazones of the corresponding bromoketones (7, 8). The syn-and antichloroacetates were identified by comparison of spectral data to those of authentic sampl...

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N,N-Dibromobenzenesulfonamide

Crouch

2008

Encyclopedia of Reagents for Organic Synthesis

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Bridged Ring Compounds. XIII.^1-3 The Reaction of N,N-Dibromobenzenesulfonamide with Bicyclo[2 2.1]heptene, Bicyclo[2.2.2]octene, and endo-Bicyclo[2.2.1]-5-heptene-2,3-dicarboxylic Anhydride

Cited by 14 publications

References 3 publications

¹H chemical shifts in NMR. Part 24—proton chemical shifts in some gem‐difunctional compounds: 3‐endo‐ and 3‐exo‐substituted norbornanones

¹H chemical shifts in NMR. Part 24—proton chemical shifts in some gem‐difunctional compounds: 3‐endo‐ and 3‐exo‐substituted norbornanones

Acid-catalyzed Ring Opening of Halo-nortricyclanes

N,N-Dibromobenzenesulfonamide

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Bridged Ring Compounds. XIII.1-3 The Reaction of N,N-Dibromobenzenesulfonamide with Bicyclo[2 2.1]heptene, Bicyclo[2.2.2]octene, and endo-Bicyclo[2.2.1]-5-heptene-2,3-dicarboxylic Anhydride

Cited by 14 publications

References 3 publications

1H chemical shifts in NMR. Part 24—proton chemical shifts in some gem‐difunctional compounds: 3‐endo‐ and 3‐exo‐substituted norbornanones

1H chemical shifts in NMR. Part 24—proton chemical shifts in some gem‐difunctional compounds: 3‐endo‐ and 3‐exo‐substituted norbornanones

Acid-catalyzed Ring Opening of Halo-nortricyclanes

N,N-Dibromobenzenesulfonamide

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Bridged Ring Compounds. XIII.^1-3 The Reaction of N,N-Dibromobenzenesulfonamide with Bicyclo[2 2.1]heptene, Bicyclo[2.2.2]octene, and endo-Bicyclo[2.2.1]-5-heptene-2,3-dicarboxylic Anhydride

¹H chemical shifts in NMR. Part 24—proton chemical shifts in some gem‐difunctional compounds: 3‐endo‐ and 3‐exo‐substituted norbornanones

¹H chemical shifts in NMR. Part 24—proton chemical shifts in some gem‐difunctional compounds: 3‐endo‐ and 3‐exo‐substituted norbornanones