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    Organic Chemistry

    Uploaded by

    Racheal Kirby
    Tutorial questions and answers

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    Organic Chemistry

    Uploaded by

    Racheal Kirby
    149 views2 pages
    Tutorial questions and answers

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    Tutorial questions and answers

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    149 views2 pages

    Organic Chemistry

    Uploaded by

    Racheal Kirby
    Tutorial questions and answers

    Copyright:

    Attribution Non-Commercial (BY-NC)
    Download as PDF, TXT or read online from Scribd
    Download as pdf or txt
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    SLE214 tutorial 6 (solutions)

    Q1. Provide the products and a reaction mechanism for the following (Only consider substitution reactions). Be sure to indicate correct stereochemistry i.e. assign R & S to starting materials and products where applicable.

    (R ) Br

    EtOH 60oC O

    EtOH is a poor nucleophile, EtOH is a polar protic solvent With a 3 o substrate you expect SN1 to dominate. Both the ( R) and the ( S) forms would be produced

    ( R) H Br

    EtS Acetone H ( S) SEt :SEt is a good nucleophile, acetone is a polar aprotic solvent With a 2 o substrate you expect SN2 to dominate.

    Q2. The best nucleophiles have lone pairs and a negative charge but are not overly basic (if they are they like to act as a base in preference). Use a table of pKa values to estimate whether the following would function as nucleophiles or bases. (pKa values for the parent acid of the anions are in red) :CN: CH3CC: 9.1 45

    CH3CH2O: 19
    N

    acetate 4.7

    phenoxide 10

    CH3S: 10.7

    HO: 15.7

    36

    62

    A pKa value in the range of 7-14 is ideal. Lower than that eg acetate is heading towards poor nucleophile and greater than that is heading towards behaving as a base. This is a guideline only solvent and substrate must be considered.

    Q3. Provide mechanism and products for the following: Clearly indicate when there would be a mixture of products.

    H H H Br H HH tBuO t BuOH

    All coloured H's are in the correct LG-C-C-H arrangement but Both blue H's are oriented in the required antiperiplanar arrangement only elimination of the top blue H will give the most substituted prod

    Elimination is definitely favoured with a sterically hindered base such as tert-butoxide, a protic solvent and a secondary substrate. Mechanism will be E2. pKa of tBuOH is about 18 so tertbutoxide is at the basic end of nucleophiles so likes to function as a base. Remember the antiperiplanar arrangement required. NOTE also that EITHER of those protons could be oriented correctly for E2 elimination, it would only take rotation around the single bond.
    EtO H Br EtOH

    Same as above, Ethoxide is a bit less basic but only just.


    H H H E2 tBuO Br t BuOH
    All coloured H's are in the correct LG-C-C-H arrangement but Both blue H's are oriented in the required antiperiplanar arrangement only elimination of the top blue H will give the most substituted prod (Zaitsevs Rule)

    EtOH No H's are available (antiperiplanar) for E2 in this conformation but it is in equilibrium with the less favoured conformational isomer below

    Br

    EtO

    H H H Br

    EtO EtOH favoured

    Blue H is the only one that can be involved in the E2 elimination therefore the product is as shown. This is a really tough question!!!!!

    Br

    EtOH H 2O, heat

    OEt +

    OH

    A mix of SN1 and E1 will occur. Hard to predict which will dominate but McMurry says SN1 is favoured in hydroxylic solvents so around 70% SN1 and 30%E1 would seem about right. There are two possible nucleophiles EtOH and H2 O. Ethanol is slightly better but SN1 prods would depend on amounts of EtOH vs H2O. This is an example of the lesser usefulness of these SN1 and E1 reactions - no steroechemical control and hard to get one single product. A decent base would give you almost 100% E2 in this instance.

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