Brominations with <i>N</i>-Bromosuccinimide and Related Compounds. The Wohl-Ziegler Reaction.

Djerassi, Carl

doi:10.1021/cr60135a004

Cited by 330 publications

(136 citation statements)

References 59 publications

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“…Installation of a bromine at the 3-methyl position on the thiophene ring was performed using Wohl-Ziegler radical conditions (Scheme 1) [31]. Briefly, a suspension of the solid polymer (1), Nbromosuccinimide and benzoyl peroxide in carbon tetrachloride was stirred at room temperature overnight.…”

Section: Resultsmentioning

confidence: 99%

Installation of a reactive site for covalent wiring onto an intrinsically conductive poly(ionic liquid)

Brombosz

Lee

Firestone

2014

Reactive and Functional Polymers

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a b s t r a c tPost-polymerization radical bromination of a nanostructured poly(ionic liquid) that selectively introduces a reactive bromo-group onto the polyalkylthiophene backbone is described. Raman and FT-IR spectroscopy proves that the bromine is successfully introduced at the 3-methyl position of the thiophene and that the molecular structure of the polymer remains largely intact with only minimal chain scission detected. FT-IR and Vis-NIR spectroscopy indicates that incorporation of the bromine induces twisting (loss of co-planarity) of the polythiophene backbone. WAXS confirms retention of an ordered lamellar structure with minor lattice spacing contraction. Cyclic voltammetry confirms spectroscopic findings that the bromination reaction yields a stable p-doped polymer. The installed bromine is susceptible to nucleophilic displacement permitting the covalent attachment of other functional molecules, such as a dialkylphosphonate. Elemental analysis of such a transformation established that 100% functionalization can be achieved. These results collectively demonstrate that post-modification of a pconjugated polymer can be used to both tune electronic and photonic properties, as well as install a chemoselective attachment point for the covalent wiring of other molecules.

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Section: Resultsmentioning

confidence: 99%

Installation of a reactive site for covalent wiring onto an intrinsically conductive poly(ionic liquid)

Brombosz

Lee

Firestone

2014

Reactive and Functional Polymers

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“…Halogenation in the bicyclo [2.2.2]octane moiety being pro hibited [11], reaction occurs in the cyclohexene ring; replacement at the 2'-methylene carbon is in-finic structure [18], as in the present example. Com parable allylic brom inations occur in diisophorones, being effected equally readily by molecular bromine or N-bromosuccinimide [19]; they are therefore accountable in terms of the familiar free radical chain mechanism [20].…”

Section: Resultsmentioning

confidence: 99%

Bicyclo[2.2.2]octane-2-spirocyclohexanes, Part 5 [1] The Action of Grignard Reagents on Spirodiisophora-3′,6-dione

Kurzer

Hawkes

1992

Zeitschrift Für Naturforschung B

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“…The ii~agnitude of this coupling constant is in agreement \\.it11 expectation (part A of Chart 2). 11 Since the two pei~tadeuterocyclohexanols resulting from cis and trans addition of DOI-I to I were available, it seemed that it was now possible to study the stereochemistry of acid-catalyzed hydration of cyclohexene. The conversion of ordinary cyclohexene to cyclol~exanol could be perforined by shaking c)rclohexene for 1 h a t 50' \\-it11 a mixture of 75y0 HzS04 and CC14.…”

Section: Results a S D Discussionmentioning

confidence: 99%

CYCLOHEXENE-3,3,6,6-d₄ A USEFUL COMPOUND FOR THE STUDY OF MECHANISM AND STRUCTURE

Wolfe¹,

Campbell²

1965

Can. J. Chem.

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The title compound (I) was prepared by Diels-Alder reaction of butadiene-1,1,4,4-d., with ethylene. The considerations which led to the synthesis of I are presented and some examples are then given of how use of I can simplify the study of, and provide new information about, a number of different kinds of problems. In the proton magnetic resonance (n.111.r.) spectra of the products of additions to I , the tertiary protons ~~s~~a l l y appear as clearly defined quartets. Since J J a n ! can be read directly from these spectra, both the stereochemistry of the additions and the conforn~ations of the products call be deduced. Thus, oxymercuration of I is clear!y a traws addition and Na/Hg reduction of the mercury takes place with retention of c o n f i g~~r a t~o~l . \hihe11 the second step is performed in D.0, the oxyn~ercuration-reduction sequence represents a convenient route for the trans addition of DOH to a double bond. Deuteroboration provided a n example of cis addition of DOH to I. Acid-catalyzed hydration of I resulted in scrambling of the d e~~t e r i u~n atoms. The value of Gn,/o~f is small; Gur/on is 600 cal/mole. The position of the double bond in a product resulting from allylic substitution of I is determined by integration of the n.m.r. spectrum. lielative to I, the possibilities are no rearrangement, 50% rearrangement, and 100% rearrangement of the double bond. The first product of allylic substitution by N-bro~nosuccinimide shows IIO rearrangement; therefore, this reaction does 11ot require a "free" radical intermediate. The structure of an adduct formed during allylic acetosylation of I by mercuric acetate (the Treibs reaction) has been determined.

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Brominations with N-Bromosuccinimide and Related Compounds. The Wohl-Ziegler Reaction.

Cited by 330 publications

References 59 publications

Installation of a reactive site for covalent wiring onto an intrinsically conductive poly(ionic liquid)

Installation of a reactive site for covalent wiring onto an intrinsically conductive poly(ionic liquid)

Bicyclo[2.2.2]octane-2-spirocyclohexanes, Part 5 [1] The Action of Grignard Reagents on Spirodiisophora-3′,6-dione

CYCLOHEXENE-3,3,6,6-d₄ A USEFUL COMPOUND FOR THE STUDY OF MECHANISM AND STRUCTURE

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Brominations with N-Bromosuccinimide and Related Compounds. The Wohl-Ziegler Reaction.

Cited by 330 publications

References 59 publications

Installation of a reactive site for covalent wiring onto an intrinsically conductive poly(ionic liquid)

Installation of a reactive site for covalent wiring onto an intrinsically conductive poly(ionic liquid)

Bicyclo[2.2.2]octane-2-spirocyclohexanes, Part 5 [1] The Action of Grignard Reagents on Spirodiisophora-3′,6-dione

CYCLOHEXENE-3,3,6,6-d4 A USEFUL COMPOUND FOR THE STUDY OF MECHANISM AND STRUCTURE

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CYCLOHEXENE-3,3,6,6-d₄ A USEFUL COMPOUND FOR THE STUDY OF MECHANISM AND STRUCTURE