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    Elimination Reaction PDF

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    The document summarizes elimination reactions, which involve removing two substituents from a molecule to form a double bond. It describes the E2 and E1 mechanisms. E2 is a one-step reaction that requires the leaving groups to be antiperiplanar. E1 is a two-step reaction involving carbocation formation. Factors like sterics, temperature, and substitution influence whether E2 or E1 occurs. The rate of E2 depends on concentrations of both reactants, while E1 depends only on the alkyl halide concentration.

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    Elimination Reaction PDF

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    shantharm
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    The document summarizes elimination reactions, which involve removing two substituents from a molecule to form a double bond. It describes the E2 and E1 mechanisms. E2 is a one-step reaction that requires the leaving groups to be antiperiplanar. E1 is a two-step reaction involving carbocation formation. Factors like sterics, temperature, and substitution influence whether E2 or E1 occurs. The rate of E2 depends on concentrations of both reactants, while E1 depends only on the alkyl halide concentration.

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    The document summarizes elimination reactions, which involve removing two substituents from a molecule to form a double bond. It describes the E2 and E1 mechanisms. E2 is a one-step reaction that requires the leaving groups to be antiperiplanar. E1 is a two-step reaction involving carbocation formation. Factors like sterics, temperature, and substitution influence whether E2 or E1 occurs. The rate of E2 depends on concentrations of both reactants, while E1 depends only on the alkyl halide concentration.

    Copyright:

    © All Rights Reserved
    Download as PDF, TXT or read online from Scribd
    Download as pdf or txt
    2K views4 pages

    Elimination Reaction PDF

    Uploaded by

    shantharm
    The document summarizes elimination reactions, which involve removing two substituents from a molecule to form a double bond. It describes the E2 and E1 mechanisms. E2 is a one-step reaction that requires the leaving groups to be antiperiplanar. E1 is a two-step reaction involving carbocation formation. Factors like sterics, temperature, and substitution influence whether E2 or E1 occurs. The rate of E2 depends on concentrations of both reactants, while E1 depends only on the alkyl halide concentration.

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    of 4

    Elimination reaction

    The reaction rate, inuenced by both the alkyl halide


    and the base (bimolecular), is second order.
    Because E2 mechanism results in formation of a
    pi bond, the two leaving groups (often a hydrogen and a halogen) need to be antiperiplanar. An
    antiperiplanar transition state has staggered conformation with lower energy than a synperiplanar transition state which is in eclipsed conformation with
    higher energy. The reaction mechanism involving
    staggered conformation is more favorable for E2 reactions (unlike E1 reactions).

    Elimination reaction of cyclohexanol to cyclohexene with sulfuric


    acid and heat [1]

    An elimination reaction is a type of organic reaction


    in which two substituents are removed from a molecule
    in either a one or two-step mechanism.[2] The one-step
    mechanism is known as the E2 reaction, and the two-step
    mechanism is known as the E1 reaction. The numbers
    do not have to do with the number of steps in the mechanism, but rather the kinetics of the reaction, bimolecular
    and unimolecular respectively.

    E2 typically uses a strong base, it needs a chemical


    strong enough to pull o a weakly acidic hydrogen.
    In order for the pi bond to be created, the
    hybridization of carbons need to be lowered from
    sp3 to sp2 .

    In most organic elimination reactions, at least one hydrogen is lost to form the double bond: the unsaturation of
    the molecule increases. It is also possible that a molecule
    undergoes reductive elimination, by which the valence of
    an atom in the molecule decreases by two. An important
    class of elimination reactions are those involving alkyl
    halides, with good leaving groups, reacting with a Lewis
    base to form an alkene. Elimination may be considered
    the reverse of an addition reaction. When the substrate
    is asymmetric, regioselectivity is determined by Zaitsevs
    rule or through Hofmann elimination if the Carbon with
    the most substituted Hydrogen is inaccessible.

    The C-H bond is weakened in the rate determining


    step and therefore a primary deuterium isotope effect much larger than 1 (commonly 2-6) is observed.
    E2 competes with the SN2 reaction mechanism.

    E2 mechanism

    Scheme 1. E2 reaction mechanism

    During the 1920s, Sir Christopher Ingold proposed a


    model to explain a peculiar type of chemical reaction;
    the E2 mechanism. E2 stands for bimolecular elimination. The reaction involves a one-step mechanism in
    which carbon-hydrogen and carbon-halogen bonds break
    to form a double bond. C=C Pi bond.

    An example of this type of reaction in scheme 1 is the


    reaction of isobutylbromide with potassium ethoxide in
    ethanol. The reaction products are isobutylene, ethanol
    and potassium bromide.

    The specics of the reaction are as follows:

    2 E1 mechanism

    E1 is a model to explain a particular type of chemical


    E2 is the rst step of elimination with a single
    elimination reaction. E1 stands for unimolecular elimitransition state.
    nation and has the following specicities.
    Typically undergone by primary substituted alkyl
    halides, but is possible with some secondary alkyl
    halides.

    It is a two-step process of elimination: ionization


    and deprotonation.
    1

    5
    Ionization: the carbon-halogen bond breaks to
    give a carbocation intermediate.
    Deprotonation of the carbocation.
    E1 typically takes place with tertiary alkyl halides,
    but is possible with some secondary alkyl halides.

    REFERENCES

    Highly substituted carbocations are more stable than


    methyl or primary substituted cations. Such stability
    gives time for the two-step E1 mechanism to occur.
    If SN1 and E1 pathways are competing, the E1 pathway can be favored by increasing the heat.

    The reaction rate is inuenced only by the concen- Specic features : 1 . Rearrangement possible 2 . Indetration of the alkyl halide because carbocation for- pendent of concentration and basicity of base
    mation is the slowest step aka rate-determining step.
    Therefore rst-order kinetics apply (unimolecular).
    Reaction usually occurs in complete absence of base 3 E2 and E1 elimination nal notes
    or presence of only a weak base (acidic conditions
    and high temperature).
    The reaction rate is inuenced by halogen's reactivity,
    iodide and bromide being favored. Fluoride is not a good
    E1 reactions are in competition with SN1 reactions
    leaving group. There is a certain level of competition
    because they share a common carbocationic interbetween elimination reaction and nucleophilic substimediate.
    tution. More precisely, there are competitions between
    A secondary deuterium isotope eect of slightly E2 and SN2 and also between E1 and SN1. Substitution generally predominates and elimination occurs only
    larger than 1 (commonly 1 - 1.5) is observed.
    during precise circumstances. Generally, elimination is
    No antiperiplanar requirement. An example is the favored over substitution when
    pyrolysis of a certain sulfonate ester of menthol:
    steric hindrance increases
    basicity increases
    temperature increases
    the steric bulk of the base increases (such as in
    Potassium tert-butoxide)
    E1 elimination Nash 2008, antiperiplanar relationship in blue

    the nucleophile is poor

    In one study [4] the kinetic isotope eect (KIE) was determined for the gas phase reaction of several alkyl halides
    with the chlorate ion. In accordance with an E2 elimination the reaction with t-butyl chloride results in a KIE of
    2.3. The methyl chloride reaction (only SN2 possible) on
    Accompanied by carbocationic rearrangement reac- the other hand has a KIE of 0.85 consistent with a SN2 reaction because in this reaction type the C-H bonds tighten
    tions
    in the transition state. The KIEs for the ethyl (0.99) and
    isopropyl (1.72) analogues suggest competition between
    the two reaction modes.
    Only reaction product A results from antiperiplanar elimination, the presence of product
    B is an indication that an E1 mechanism is
    occurring.[3]

    4 See Also
    Scheme 2. E1 reaction mechanism

    E1cB-elimination reaction

    An example in scheme 2 is the reaction of tertbutylbromide with potassium ethoxide in ethanol.

    5 References

    E1 eliminations happen with highly substituted alkyl


    halides due to 2 main reasons.
    Highly substituted alkyl halides are bulky, limiting
    the room for the E2 one-step mechanism; therefore,
    the two-step E1 mechanism is favored.

    [1] Organic Syntheses I:185 http://orgsynth.org/orgsyn/pdfs/


    CV1P0183.pdf
    [2] March, Jerry (1985), Advanced Organic Chemistry: Reactions, Mechanisms, and Structure (3rd ed.), New York:
    Wiley, ISBN 0-471-85472-7

    [3] Nash, J. J.; Leininger, M. A.; Keyes, K. (April


    2008). Pyrolysis of Aryl Sulfonate Esters in the
    Absence of Solvent: E1 or E2?
    A Puzzle for
    the Organic Laboratory. Journal of Chemical Education 85 (4): 552. Bibcode:2008JChEd..85..552N.
    doi:10.1021/ed085p552.
    [4] Stephanie M. Villano, Shuji Kato, and Veronica M. Bierbaum (2006). Deuterium Kinetic Isotope Eects in GasPhase SN2 and E2 Reactions: Comparison of Experiment
    and Theory. J. Am. Chem. Soc. 128 (3): 736737.
    doi:10.1021/ja057491d. PMID 16417360.

    6 TEXT AND IMAGE SOURCES, CONTRIBUTORS, AND LICENSES

    Text and image sources, contributors, and licenses

    6.1

    Text

    Elimination reaction Source: http://en.wikipedia.org/wiki/Elimination%20reaction?oldid=636465402 Contributors: Michael Hardy,


    Karlwick, RedWolf, Naddy, Hadal, Polychrome, Robodoc.at, D3, Icairns, Sam Hocevar, Shudog, Arcadian, Keenan Pepper, Ceyockey,
    LOL, Jfx319, V8rik, Bubbachuck, YurikBot, Person unknown, Esprit15d, GraemeL, Itub, SmackBot, Edgar181, Lovecz, MalafayaBot,
    DMacks, Marcipangris, Pedrora, Lottamiata, Briansal, Rieman 82, Thijs!bot, Nonagonal Spider, JAnDbot, MER-C, Sushant gupta, Ovy,
    R'n'B, CommonsDelinker, LordAnubisBOT, DorganBot, Mikearmet, Lears Fool, Lamro, OKBot, Anchor Link Bot, ClueBot, DragonBot,
    SilvonenBot, Addbot, DOI bot, LaaknorBot, Xerxes b, Luckas-bot, Yobot, Xqbot, Elvim, GrouchoBot, Brandon5485, Shadowjams, Jupiterccnetcom, Citation bot 1, Park4223, Thecurran91, Russot1, TjBot, Mrseanski, EmausBot, Tobraider, Orange Suede Sofa, ChuispastonBot,
    Rmashhadi, ClueBot NG, Bibcode Bot, Gladissk, ChrisGualtieri, Physchem 13, Priyanka Sandhu, Monkbot, Owais Khursheed, Mtalley90,
    Y-S.Ko and Anonymous: 77

    6.2

    Images

    File:E1-eliminationNash2008.svg Source: http://upload.wikimedia.org/wikipedia/commons/f/fd/E1-eliminationNash2008.svg License:


    CC-BY-SA-3.0 Contributors: Transferred from en.wikipedia; transferred to Commons by User:Quadell using CommonsHelper. Original
    artist: Original uploader was V8rik at en.wikipedia
    File:E1_Elimination_Reaction.png Source: http://upload.wikimedia.org/wikipedia/commons/f/fe/E1_Elimination_Reaction.png License: CC-BY-SA-3.0 Contributors: Originally from en.wikipedia; description page is/was here. Original artist: Original uploader was
    V8rik at en.wikipedia
    File:E2_Elimination_Reaction.png Source: http://upload.wikimedia.org/wikipedia/commons/d/d6/E2_Elimination_Reaction.png License: CC-BY-SA-3.0 Contributors: Originally from en.wikipedia; description page is/was here. Original artist: Original uploader was
    V8rik at en.wikipedia
    File:EliminationReactionCyclohexene.svg
    Source:
    http://upload.wikimedia.org/wikipedia/commons/4/44/
    EliminationReactionCyclohexene.svg License: CC-BY-SA-3.0 Contributors: Transferred from en.wikipedia; transferred to Commons by User:Choij using CommonsHelper.
    Original artist: V8rik (talk). Original uploader was V8rik at en.wikipedia
    File:Wikiquote-logo.svg Source: http://upload.wikimedia.org/wikipedia/commons/f/fa/Wikiquote-logo.svg License: Public domain
    Contributors: ? Original artist: ?

    6.3

    Content license

    Creative Commons Attribution-Share Alike 3.0

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