Questions tagged [rearrangements]
For questions about specific rearrangements within organic chemistry.
53
questions
4
votes
0answers
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Beckmann Rearrangement in cyclic compounds
Consider 1-indanone:
I am supposed to find the rearrangement product on treating this with hydroxylamine (which gives an oxime) and then $\ce{H+}$ (with heat). I am aware of the mechanism of Beckmann ...
2
votes
0answers
37 views
Products of the reaction between cyclohexanone and N-bromosuccinimide
Problem
Treating cyclohexanone with N-bromosuccinimide in the presence of carbon tetrachloride gives A. A on treatment with aqueous KOH gives B. Deduce the structures of A and B.
Solution
Questions
...
0
votes
0answers
26 views
Reliance of migratory aptitude on steric hindrance and its effect on rate of reaction
I've learnt that the migratory aptitude of phenyl is greater than that for methyl, for example.
But how do I find the order of the same for any given 2 groups, like $\ce{Cl-}$ and $\ce{PhCH2CH2CH3-}$, ...
1
vote
1answer
44 views
How does temperature and other factors affect sigmatropic rearrangements?
The image below shows a [3,3] sigmatropic rearrangement. My question is why does the increased temperature favour the right side? The arrangement is technically the same except for the methyl groups ...
2
votes
0answers
42 views
Show the mechanism of the Pinacol-Pinacolone Rearrangement reaction [duplicate]
In the reactant, due to $\ce{H+}$ ion, a positive charge will be created by removing water in place of the rightmost $-\ce{OH}$.
But then how will it give such a product. I cant see any way to make ...
1
vote
1answer
44 views
Carbocation rearrangement
I am dealing with some basic reactions in organic chemistry. One of these is the acid reflux of alcohols. Something I came across was hydride shifts. I know how and why they occur, but I don't ...
1
vote
0answers
55 views
Hydrogen isotope effect on methyl shift
Consider this typical 1,2 methanide shift in a carbocation:
Which isotopic form of methanide ($\ce{CH3, CD3, or CT3}$) would migrate from secondary carbocation to form more stable tertiary ...
0
votes
1answer
83 views
Baeyer-Villiger Oxidation restricted to Ketones
According to Wikipedia, Baeyer Villiger oxidation occurs at the electron deficient oxygen site, with elimination of the carboxylate ion, and migration of an R group. But it is restricted to ketones ...
12
votes
1answer
153 views
Mechanism for the addition of hydrogen iodide to 3,3‐dimethylbut‐1‐yne
The following reaction mechanism was given as a solution to a solved problem in my textbook1 for the addition of hydrogen iodide to 3,3‐dimethylbut‐1‐yne:
It can be seen that that 2,2-diiodo-3,3-...
0
votes
0answers
60 views
Extent of multiple hydride shifts in a carbocation
Take this example:
Multiple hydride shifts are possible only if in each step, the formed intermediate is more stable than the previous one.
(1) to (2) converts $2^\circ$ carbocation to $3^\circ$ ...
1
vote
1answer
147 views
Acid catalysed dehydration of alcohol with a bicyclo group
Pathway 1: Rate determining step is the formation of carbocation. In this pathway, a conjugated tertiary carbocation is generated as an intermediate.
Pathway 2: One of the resonance form of ...
0
votes
1answer
79 views
Acid catalysed dehydration of 5-methylidenecyclopent-2-en-1-ol [closed]
I think the following reaction is NOT possible.
I could not find a mechanism for ring expansion. Is ring expansion possible in any way?
Is the following mechanism correct?
0
votes
2answers
69 views
Dehydration of primary alcohol with a cyclobutadiene substituent [closed]
Note: Primary alcohol will follow E2 mechanism, therefore, removal of protonated water and proton (RDS) shall proceed in a single step in the above mechanism.
My questions are:
1- According to ...
3
votes
1answer
451 views
Beckmann rearrangement v/s dehydration of Oximes
In the above question, A is an oxime, which is then reacted with phosphorus pentoxide. Now, phosphorus pentoxide is both a dehydrating reagent and a reagent used for Beckmenn rearrangement, but which ...
0
votes
1answer
49 views
Ring expansion in cyclo compounds
In the following reaction, why does ring expansion not take place?
Mechanism that was the correct one:
In the second step when there is a protonated carbon the ring should expand to become 6 ...
0
votes
1answer
107 views
Preparation of Grignard reagent. Free radical rearrangement
Mechanism of formation of Grignard Reagent
$$\ce{R-X + ^.Mg^. ->[\text{r.d.s.}] R^. + ^.Mg+X-} $$
$$\ce{R^. + ^.Mg+X- -> R-Mg+X-} $$
As the mechanism of preparation of Grignard reagent suggests,...
1
vote
0answers
95 views
What the product of this reaction?
The reaction is as follows, with (i) being my answer, and (ii) being the correct answer in the book.
My question is why is the product (ii) formed here and elimination not favoured here? I think that ...
5
votes
1answer
268 views
Hydrolysis of (chloromethyl)cyclopropane: Is but-3-en-1-ol a possible product?
This is from one of the practice papers for the JEE , asks for possible hydrolysis products of (chloromethyl)cyclopropane .
Product A happens to be due to stability of cyclopropyl methyl carbocation.
...
1
vote
0answers
119 views
Predict the products of the following reactions with Mechanism [closed]
1
My Attempt : The correct answer is C. I tried rearranging similar to claisen rearrangement but I have no clue how to go forward. I know that option A is wrong and that the product is pretty easily ...
2
votes
1answer
125 views
Why does ring contraction take place in Wagner–Meerwein rearrangement?
An example of Wagner–Meerwein rearrangement given in my textbook is substitution by $\ce{AgNO2}$ in iodocyclohexane. One of the product, cyclopentylnitromethane is through ring contraction.
I don't ...
-1
votes
1answer
39 views
Rearrangement of 1,1-Dichloro-1a,9b-dihydro-1H-cyclopropa[l]phenanthrene on heating
Due to angle strain , the three membered ring is not stable. So i think it would break and kick out one of the chlorine atoms resulting in the formation of a carbene. But i don't know how to proceed ...
0
votes
0answers
21 views
What is a non-empirical explantation of why 1-3 methyl shifts do not occur?
How could you explain why we never see 1-3 methyl shifts? Most sources just say it is really rare, but I was wondering if you could perhaps apply orbital selection rules or a frontier orbital argument....
4
votes
1answer
67 views
Is the Beckmann Rearrangement technically an “SN2” reaction at an “sp2” center?
Below is the mechanism from this link of the Beckmann Rearrangement.
In the alkyl migration step, the alkyl group migrates simultaneously as the $\ce{H2O}$ leaving group is expelled. This seems as ...
9
votes
2answers
293 views
Photochemical rearrangement of 4,4‐diphenylcyclohexa‐2,5‐dien‐1‐one
I can see how the option A and B are correct as it is just a standard dienone–phenol type reaction which involves a phenyl shift. However, the given answer is A, B, C and D.
I do not see how C and D ...
7
votes
1answer
155 views
Does the nitrogen atom move with in the molecule in an ammonia maser, or does the molecule flip?
This intriguing answer to Can reactions produce microwave or radio wave radiation? says (in part):
An ammonia maser qualifies as an inorganic RF-emitting reaction. As the nitrogen changes position in ...
0
votes
0answers
39 views
Which of the following compound will undergo rearangement?
Question
Attempt
I believe the answer should be B,C and D. In C and D the oxyge(or Nitrogen in D) can rearange by donating lone pair to carbocation.
But the books answer says B. Where am I wrong. ...
7
votes
1answer
295 views
Elimination of bromine with sodium iodide and electrocyclization
I've been trying to solve the following reaction scheme for a while now and I am having trouble especially with the products E and F.
For product D I got the following, but I'm unsure about ...
2
votes
2answers
174 views
Anti-Markovnikov addition of HCl
The following reaction has been troubling me for a while now.
Since peroxides won't give the anti-Markovnikov product when used with HCl, I cannot think of any reagents that would result in the ...
-1
votes
1answer
111 views
Unable to form the product formed via rearrangement
Ok so I first reacted one of the carbonyl groups with NH2OH to form an oxime. And then a Beckmann rearrangement takes place followed by tautomerism. Then the lone pair on nitrogen did an ...
5
votes
1answer
292 views
Acid-catalysed isomerisation of phenyl epoxide to aldehyde
How does $\ce{H3O+}$ cause the formation of an aldehyde from the following epoxide?
I thought that the epoxide would undergo opening to form a 1,2-diol, as illustrated below. Am I wrong?
1
vote
1answer
172 views
Intramolecular Reaction with carbocation rearrangement
I came across a question recently which is as follows,
I came up with a mechanism but I am stuck at a step as I am unable to reason out the driving force.
Step(3) has a hydride shift and its next ...
1
vote
1answer
424 views
Question on ring expansion
In the orange box, I think that the blue-carbon should be a carbocation instead. So, option A should be correct.
But, the answer is B. Why is it so?
8
votes
3answers
1k views
Reaction mechanism of rearrangement
I am currently studying for my organic chemistry exam, but there is one problem I do not understand. Unfortunately, I do not have any solutions.
See image for the problem.
My first thought was the ...
3
votes
1answer
127 views
Rearrangement considerations in feasibility of SN1 in given reactants
I have been asked to compare the feasibility of Unimolecular Nucleophilic Substitution ($\mathrm{S_N1}$) in the following question.
I have received instruction that the reaction will be feasible only ...
6
votes
2answers
1k views
Tiffeneau–Demjanov rearrangement products
With reference to the paper McCasland, G. E. Pinacolic Rearrangements of Epimeric Aminocyclanols. J. Am. Chem. Soc. 1951, 73 (5), 2293–2295 DOI: 10.1021/ja01149a110. (ResearchGate link). It states ...
4
votes
4answers
259 views
8a-methyl-1,2,3,4,4a,8a-hexahydronaphthalen-4a-ylium carbocation rearrangement
In this reaction after the attack of lone pairs on $\ce{H+}$ ions, a stable $3^{°}$ carbocation is formed. But seeing the six membered ring and the double bonds already present, I can't help but think ...
4
votes
1answer
426 views
Mechanism of Fritsch–Buttenberg–Wiechell rearrangement
The following reaction was given, which uses potassium t-butoxide.
The solution to this problem was given as follows:
Step 1 is the attack of strong base, t-butoxide, on the vinyl proton.
Step 2 ...
1
vote
0answers
516 views
Retention of configuration in Hofmann rearrangement
Why is there a retention of configuration in Hofmann bromamide degradation/Hofmann rearrangement?
I would think that there should be an inversion of configuration due to the migration of alkyl group ...
2
votes
2answers
700 views
Rearrangment during alkyne synthesis
What I have got as (G) is this.
$\hskip1in$
My questions
How the rearrangement from (G) to $non-1-yne$ can happen i.e. its mechanism?
Why Sodium Amide in particular yield terminal alkyne, unlike ...
2
votes
0answers
135 views
Ring contraction in benzilic rearrangement
Wikipedia says that,
Benzilic acid rearrangement occurs with ring contraction when used on cyclic diketones.
But gave no explanation, can you please elaborate on this with some mechanism. One ...
11
votes
1answer
691 views
Formamide and Hoffmann Bromamide Reaction
I encountered a problem to identify the compound which does not give Hoffmann bromamide degradation reaction. One of the options was formamide, and it was given as the answer.
Why can't formamide ...
2
votes
1answer
51 views
Determining ratio of competing fragmentation processes in mass spectrometry
In a photoionization experiment, three photons of wavelength 266 nm were absorbed by a neutral molecule of 6-methyl-2-heptanone. If the kinetic energy of the electron removed during ionization is 1.4 ...
4
votes
1answer
579 views
The oxidation of aldehydes and alpha-diketones with peroxy compounds
Recently, I have been reading up on the Baeyer-Villiger (BV) oxidation. The oxidation is most commonly discussed for ketones. However, the oxidation also works for aldehydes and $\alpha$-diketones (...
0
votes
1answer
183 views
Benzilic acid rearrangement
I'm in need for the exact mechanism of the above reaction. I attempted some tries(mentioned in the mechanism above) and I felt the yield quite unsatisfactory.
- the last step remains stuck in an ...
5
votes
0answers
301 views
Shouldn't the 5-membered ring expand to a six membered one in this nucleophilic addition reaction?
I am dealing with a problem involving addition of $\ce{HCl}$ to a ring:
According to what I think, the ring should expand to a six-membered following carbocation formation at the tertiary site, as a ...
0
votes
1answer
391 views
Reaction mechanism for the conversion of acyl hydrazide to acyl azide
How is an an acyl hydrazide converted into an acyl azide in the presence of $\ce{HNO2}$? According to me, the $\ce{-NH2}$ group of hydrazide will get converted into $\ce{-N2+}$ through $\ce{HNO2}$. ...
9
votes
1answer
1k views
Ring contraction when cyclohexene oxide is treated with methyl Grignard
My book writes that:
Recall that epoxides rearrange with Lewis acids in a pinacol-like fashion, and that Grignard reagents in THF exist in the following equilibrium:
I approached this ...
1
vote
0answers
92 views
Number of products on dehydrobromination
Question:
The total number of alkene products possible from the dehydrobromination of 3-bromo-3-cyclopentylhexane using alcohol KOH is :
This question was asked here before but I am getting more ...
3
votes
0answers
234 views
Major product of isomerization reaction
I am trying to come up with a logical mechanism for the following transformation, where 2-methylenecyclobutan-1-ol is converted to cyclopentanone under acidic conditions:
What I have tried to do was ...
10
votes
2answers
851 views
Can a six member ring expand to achieve octet completion to stabilize a carbocation?
(Probably unnecessary background: I came up with this carbocation while predicting the major product of $\ce{NaNO2/HCl}$ with 1-(methylamine)cyclohexan-1-ol)
Will the following carbocation ...
