DAT organic chemistry odyssey chapter 13 question 6,
so in the reaction scheme, i understand that the first reagent will cause a markovnikov addition of OH and H without any carbocation shifts.
the second reagent will convert the secondary alcohol into the ketone.
but what i don't understand is the addition of NH3 to a ketone. I have been told from watching organic chemistry lectures at UC irvine that NH3 when added to an aldehyde or ketone will generate a very unstable "imine" and you typically wouldn't see this reaction. So in theory, wouldn't the correct answer be a ketone?
DAT organic chemistry odyssey chapter 13 question 38,
why is the answer A not D?
DAT organic chemistry odyssey chapter 12 question 10,
why is the group a deactivating group? You clearly see that the sulfur attached to the benzene has a lone pair, so wouldn't this mean that its an electron donor group?
DAT organic chemistry odyssey chapter 12 question 13,
Is the difference between electron pair A and electron pair D purely based on % s character?
DAT organic chemistry odyssey chapter 12 question 36,
why are acetals ortho/para directors if the atom directly bound to the benzene has no lone pairs and has the two oxygen groups directly attached? Is it because the dipoles cancel out and therefore you can treat it like an "alkyl group"?
Also just a general question from the substitution reactions chapters:
If you have a secondary alkyl halide and you react it with a non-bulky but strong base, I know you get a mixture of E2 and SN2. Is E2 favored over Sn2 though?
For example (i am referencing organic chem odyssey problems): chapter 8 question 33 (the Iodine bound to the cyclohexane undergoes E2) and chapter 8 question 9 (the iodine bound to cyclopentane undergoes Sn2 even though there is beta branching from the adjacent methyl group). Just curious on the rationale for the two questions why one is favored over the other
Ch 13 problem #6.... The imine indeed wouldn't be stable.....in the sense of isolating it.....it would be reduced down rapidly. However.... the question ask for the product formed.....Go with the imine.
Ch 13...#38......This reaction illustrates the RACEMIZATION of a ketone in base. Alpha hydrogens are replaced with deuteriums. This is an excellent way to introduce an isotopic label. The key intermediate is the enolate anion......upon reforming the carbonyl group, a D can come in from top or bottom face....thus giving the racemate. The carbonyl group STAYS,,,,,this is a more stable bond than if it was destroyed.
Ch 12 problem #10..... Great question. Wow,,,,You are good. Charged molecule will destabilize the transition state,,,,,more for the ortho and para pathways,,,less for meta,,,,hence the meta pathways dominates. The lone pair would represent d orbital electrons.....this would not contribute to intermediate stabilization. Carbon uses 2p orbitals,,,,S uses 3 p orbitals,,,,,the orbital size not the greatest for overlap. Thus the alkyl sulfonium group is a META director !!!
Chapter 12 problem #36 Acetals are simply Diethers,,,,,,This is a very nice way to transform a meta director such as acetyl into an O/P director !!!!! There is still a Hydrogen that can participate in a hyperconjugative effect,,,,,draw it out......thus this can help stabilize the transition state for ortho and para pathways. Great question....wow.
For the GENERAL QUESTION......There is always a competition set up between SN2 and E2 on secondary halides. I have been most successful using HEAT ...reflux,,,,,,,to drive more E2 product. More heat allows one to do more bond breaking and forming. In a problem such as Problem 33, Chap In Chapter 8., #33......I suppose I should have added heat,,,,to avoid confusion. As a general rule of thumb....A secondary or tertiary halide treated with a strong base such as methoxide, ethoxide, amide,,,,,,,,gives more E2. Although a generalization,,,,a nice rule of thumb. In Chapter 8, problem #9....the minute you see SULFUR,,,,,think SN2 !!! Sulfur is not a good base,,,,but a GREAT nucleophile,,,,,,,and LOVES to do SN2....cyanide as well. Recall, a strong nucleophile favors Sn2,,,,,,
Hope this helps.
Dr. Jim Romano