Chapter 11 Ppt

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Chapter 11 Ppt
2014-01-22 11:13:18
CHM 202
Organic Chemistry
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  1. What is the product from R-OH through the below techniques?
    1) dehydration
    2) oxidation
    3) substitution
    5) esterification
    6) tosylation
    7) form alkoxide; R'X
    • 2) alkene
    • 2) ketones, aldehydes, acids
    • 3) halides
    • 4) alkanes
    • 5) esters
    • 6) tosylate esters
    • 7) ethers
  2. Explain the oxidation of alkanes.
    alkane oxidized to alkene oxidized to alkyne

    alkane oxidized to alcohol oxidized to ketone/ aldehyde oxidized to carboxylic acid

    alkane oxidized to chloroethane oxidized to dichloroethane oxidized to trichloroethane

    alkane oxidized to amine (NH2)--> NH--> CN
  3. oxidation of secondary alcohols with Cr(VI)

    What is the mechanism?
    leads to a ketone

    secondary alcohol + chromic acid---> chromate ester--> ketone
  4. Oxidation of primary alcohols with chromic acid
    1) to aldehydes
    2) to carboxylic acids
    • 1) DMP, Swern Oxidation, PCC
    • 2) chromic acid and NaOCl
  5. __is a complex of chromium trioxide, pyridine, and HCl.
    Oxidizes primary alcohols to __.Oxidizes secondary alcohols to __
    • PCC 
    • aldehydes
    • ketones
  6. What do tertiary alcohols get oxidized to?
    nothing; they cannot be oxidized
  7. Tertiary Alcohols:
    Caron does not have __, so oxidation is difficult and involves the breakage of a __.
    Chromic acid test is for __because tertiary alcohols do not react. __ color of Cr(VII) turns __- Cr(III); tertiary alcohol is not oxidized, therefore __.
    • hydrogen
    • C—C bond
    • primary and secondary alcohols 
    • Orange 
    • green 
    • no color change
  8. •__ (household bleach) can oxidize alcohols without heavy metals or generating hazardous waste.

    This is a much better option for acid-sensitive compounds
    Sodium hypochlorite
  9. •__, with __and __, oxidizes 2° alcohols to __and 1° alcohols to __(same as __). This reaction is called the __.
    • Dimethylsulfoxide (DMSO)
    • oxalyl chloride 
    • hindered base
    • ketones
    • aldehydes
    • PCC
    • Swern Oxidation
  10. Oxidation summary of primary:
    R-OH + Chromic acid and NaOCl --> carboxylic acid

    R-OH + PCC --> aldehyde

    R-OH + DMP, DMSO (Swern) --> aldehyde
  11. Reduction Summary
    Reduction of aldehyde or ketone to alcohol--> NaBH4 and LiAlH4

    Reduction of carboxylic acid or ester--> LiAlH4

    Reduction by Raney Nickel
  12. Conversion of alcohol into a leaving group
    - form tosylate (p-TsCl, pyridine)

    - use strong acid (H3O+)

    - convert to alkyl halide (HX, SOCl2, PBr3)
  13. How to Form p-Toluenesolfonate esters
    alcohol + TSOH

    (R-O-HHO-Ts <---> R-O-Ts + H2O)
  14. Substitution and Elimination Reactions using Tosylates:
    Attack by a nucleophile (back side attack) displaces the leaving group and adds the nucleophile in substitution

    Attack by a base deprotonates the molecule, moving the electrons to become a double bond, causing the OTs to leave
  15. R-OTs + LiAlH4--> 

    R-OTs + R'-O- -->
    R-H and -OTs

    R-O-R' + -OTs
  16. Base to use p-TsCl with pyridine
    R-OHCl-Ts---> ROTs + HCl
  17. Reduction of alcohols
    dehydrate with concentrated H2So4 then add H2

    CH3-CH2-OH ---(H2SO4)--> CH2=CH2--- (H2, Pt)--> CH3-CH3
  18. Alcohols to Alkyl Halides:
    - Tertiary

    - Secondary
    (CH3)3-C-OH + HX (HCl, HBr)---> (CH3)3-CX: rapid Sn1 (forms a tertiary carbocation)

    R2-CH-OH + HX ---> R2-CH-X
  19. Reaction of alcohols with acids:

    -The __ is protonated by an __ to convert it into a good leaving group (H2O)

    - Once the alcohol is protonated, a __ or __ can take place.
    • hydroxyl group
    • acid
    • leaving group
    • substitution
    • elimination
  20. Reaction of alcohols with acids:

    R-O-H + H+ ---> _____ ----> _____
    R-O-H2 + X- ----> R_X
  21. Reactions of alcohols with Hr

    1) ___ of alcohol is protonated

    2) ___ is good LG

    3) __ and __ react with Br- via __.

    4) __ react via __.


    • tertiary and secondary alcohols 
    • Sn1

    primary alcohols Sn2
  22. What is the Lucas Test? Why is it used?
    It is the formation of two separate layers when a reaction occurs with an alkyl bromide 

    the Lucas reagent is utilized in a reaction to form the alkyl halide (HCl + ZnCl2)

    Secondary react with the Sn1 mechanism, as do tertiary

    Primary react with the Sn2 (slow)

    • The Lucas Test:
    • tertiary react less than a minute
    • secondary react 1-5 minutes
    • primary take forever to react
  23. Sn2 reaction with the Lucas Reagent:

    1) __ react with the Lucas reagent by the Sn2 mechanism

    2) Reaction is very slow. The reaction can take from __ to __.
    primary alcohols

    • several minutes
    • several days
  24. Other qualitative tests:

    - Alcohols
    - Alkenes
    With chromic acid, primary and secondary go from orange to green/blue

    alkenes: reddish-brown--> colorless
  25. Primary and secondary alcohols: best to use what to make alkyl halides?

    All are __.
    CH3-OH ---> SOCl2---> CH3-Cl

    CH3-OH ---> PBr3--> CH3-Br

    CH3-OH ---> CH3-I
  26. Thionyl Chloride mechanism in pyridine is __. What is the mechanism?
    Sn2 inversion

    CH3-OH --> CH3-OH-SO(Cl2)----> CH3-OH-SOCl + -H+ ---> CH3-O-SOCl + Cl- ----> CH3-Cl
  27. Dehydration of alcohols:
    1) Alcohol dehydration generally takes place through the __.

    2) __ are possible. 

    3) The rate of the reaction follows the same rate as the ease of formation of __: __

    4) __ rearrange, so this is not a good reaction for coverting __ into __.
    E1 mechanism




    primary alcohols

    primary alcohols 

  28. __ is faster than the loss of H+.
    methide shift
  29. Esterification:

    (5 of them)
    Fischer: Alcohol + carboxylic acid

    tosylate esters

    sulfate esters

    nitrate esters

    phoshate esters
  30. Fischer Esterification:

    Reaction of an __ and __ produces an ester.

    ___ is a catalyst.

    The reaction is an equilibrium between __ and __, and for this reason the __ is seldom used to prepare esters.
    alcohol and a carboxylic acid

    sulfuric acid

    starting materials and products

    Fischer esterification
  31. Fischer Esterification Method:
    R-O-H-O-C=OR' <--> R-O-C=OR' + H-O-H
  32. Nitrate esters:

    The best-known nitrate ester is __, whose systematic name is __.

    __ results from the reaction of glycerol (1,2,3-propanetriol) with three molecules of nitric acid.
    • nitroglycerine
    • glyceryl trinitrate

    Glyceryl nitrate
  33. __ temporarily convert reactive functional groups into unreactive groups in a simple, high-yielding reaction.
    protecting groups