Possible nonclassical ion from a bicyclic system8a-methyl-1,2,3,4,4a,8a-hexahydronaphthalen-4a-ylium carbocation rearrangementRearrangement of 8a-ethyl-1,3,4,8a-tetrahydronaphthalen-4a(2H)-olHydrolysis of 4-chloro-3,3-dimethylbut-1-ene forms which products much faster than primary alkyl halides?Comparison of rate of dehydration of primary, secondary & tertiary alcohols on cyclohexaneIs this reaction of 4-chloro-1,1-dimethylcyclohexane SN1, SN2, E1, or E2?Why can't a nucleophile attack the intermediate of an electrophilic aromatic substitution?Is a sequence of two Wagner-Meerwein rearrangements possible?Ring expansion in the reaction of (hydroxymethyl)cyclobutane and HBrIn the addition of HBr to isoprene why does the less stable carbocation form?How is more than one pinacolone is possible?Does rearrangement occur in Friedel Crafts alkylation or not?Is rearrangement possible in cyclic bromonium ion?
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Possible nonclassical ion from a bicyclic system
8a-methyl-1,2,3,4,4a,8a-hexahydronaphthalen-4a-ylium carbocation rearrangementRearrangement of 8a-ethyl-1,3,4,8a-tetrahydronaphthalen-4a(2H)-olHydrolysis of 4-chloro-3,3-dimethylbut-1-ene forms which products much faster than primary alkyl halides?Comparison of rate of dehydration of primary, secondary & tertiary alcohols on cyclohexaneIs this reaction of 4-chloro-1,1-dimethylcyclohexane SN1, SN2, E1, or E2?Why can't a nucleophile attack the intermediate of an electrophilic aromatic substitution?Is a sequence of two Wagner-Meerwein rearrangements possible?Ring expansion in the reaction of (hydroxymethyl)cyclobutane and HBrIn the addition of HBr to isoprene why does the less stable carbocation form?How is more than one pinacolone is possible?Does rearrangement occur in Friedel Crafts alkylation or not?Is rearrangement possible in cyclic bromonium ion?
$begingroup$
In this question a bicycling alcohol is reacted with acid to make what appears to be a tertiary carbocation, and the OP asked whether it could become aromatic. The given answer suggests it could be, but only if a nonclassical ion is formed. So, does that happen?
The substrate is 8a-methyl-1,3,4,8a-tetrahydronaphthalen-4a(2H)-ol.
organic-chemistry carbocation
asked 9 hours ago
Oscar LanziOscar Lanzi
17k12853
$endgroup$
add a comment |
$begingroup$
In this question a bicycling alcohol is reacted with acid to make what appears to be a tertiary carbocation, and the OP asked whether it could become aromatic. The given answer suggests it could be, but only if a nonclassical ion is formed. So, does that happen?
The substrate is 8a-methyl-1,3,4,8a-tetrahydronaphthalen-4a(2H)-ol.
organic-chemistry carbocation
asked 9 hours ago
Oscar LanziOscar Lanzi
17k12853
$endgroup$
$begingroup$
Thanks for getting the name. IUPAC convention confuses me more than actual chemistry!
$endgroup$
– Oscar Lanzi
3 hours ago
add a comment |
$begingroup$
In this question a bicycling alcohol is reacted with acid to make what appears to be a tertiary carbocation, and the OP asked whether it could become aromatic. The given answer suggests it could be, but only if a nonclassical ion is formed. So, does that happen?
The substrate is 8a-methyl-1,3,4,8a-tetrahydronaphthalen-4a(2H)-ol.
organic-chemistry carbocation
asked 9 hours ago
Oscar LanziOscar Lanzi
17k12853
$endgroup$
In this question a bicycling alcohol is reacted with acid to make what appears to be a tertiary carbocation, and the OP asked whether it could become aromatic. The given answer suggests it could be, but only if a nonclassical ion is formed. So, does that happen?
The substrate is 8a-methyl-1,3,4,8a-tetrahydronaphthalen-4a(2H)-ol.
organic-chemistry carbocation
organic-chemistry carbocation
asked 9 hours ago
Oscar LanziOscar Lanzi
17k12853
asked 9 hours ago
Oscar LanziOscar Lanzi
17k12853
edited 3 hours ago
Oscar Lanzi
asked 9 hours ago
Oscar LanziOscar Lanzi
17k12853
asked 9 hours ago
Oscar LanziOscar Lanzi
17k12853
asked 9 hours ago
Oscar LanziOscar Lanzi
17k12853
17k12853
$begingroup$
Thanks for getting the name. IUPAC convention confuses me more than actual chemistry!
$endgroup$
– Oscar Lanzi
3 hours ago
add a comment |
$begingroup$
Thanks for getting the name. IUPAC convention confuses me more than actual chemistry!
$endgroup$
– Oscar Lanzi
3 hours ago
$begingroup$
Thanks for getting the name. IUPAC convention confuses me more than actual chemistry!
$endgroup$
– Oscar Lanzi
3 hours ago
$begingroup$
Thanks for getting the name. IUPAC convention confuses me more than actual chemistry!
$endgroup$
– Oscar Lanzi
3 hours ago
add a comment |
2 Answers
2
active
oldest
votes
$begingroup$
I don't think it is necessary to consider a mechanism with a nonclassical carbocation. It would undergo normal rearrangement with a 1,2-methide shift within the same ring. See the mechanism I posted in previous question you were directing to:
Answer to this question would support for my mechanism.
answered 6 hours ago
Mathew MahindaratneMathew Mahindaratne
8,2991131
$endgroup$
1
$begingroup$
So the answer seems to be "No". Fair enough.
$endgroup$
– Oscar Lanzi
3 hours ago
add a comment |
$begingroup$
While there are examples of 1,2-methide shifts, this question has an uncanny resemblance to the dienone-phenol rearrangement whose mechanism was first elucidated by Woodward and Singh in 1950. Dienone 1 under acidic conditions undergoes rearrangement to phenol 6 and not, based on earlier speculation, to phenol 4. The direct 1,2-methide shift (2b --> 3) does not occur but rather the reaction proceeds through the spiro carbocation 5. continued 
Applying this approach to the carbocation 7 generated from the alcohol in this question, spiro carbocation 8 forms the predicted tetrahydronaphthalene 10. One way to distinguish between the two mechanisms is via a labeling experiment. All of the carbon label in 7 will retain its location as the red star in 10 if the 1,2-methyl shift mechanism applies. The spiro mechanism will partition the label ~50:50 between the two ring benzylic carbons. For related studies, see reference 2.
1) R. B. Woodward and T. Singh, J. Am. Chem. Soc., 1950, 72, 494.
2) A. J. Waring, J. H. Zaidi and J. W. Pilkington, J. Chem. Soc, Perkin Transactions I, 1981, 1454.
answered 2 hours ago
user55119user55119
4,51711242
$endgroup$
add a comment |
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2 Answers
2
active
oldest
votes
2 Answers
2
active
oldest
votes
active
oldest
votes
active
oldest
votes
$begingroup$
I don't think it is necessary to consider a mechanism with a nonclassical carbocation. It would undergo normal rearrangement with a 1,2-methide shift within the same ring. See the mechanism I posted in previous question you were directing to:
Answer to this question would support for my mechanism.
answered 6 hours ago
Mathew MahindaratneMathew Mahindaratne
8,2991131
$endgroup$
1
$begingroup$
So the answer seems to be "No". Fair enough.
$endgroup$
– Oscar Lanzi
3 hours ago
add a comment |
$begingroup$
I don't think it is necessary to consider a mechanism with a nonclassical carbocation. It would undergo normal rearrangement with a 1,2-methide shift within the same ring. See the mechanism I posted in previous question you were directing to:
Answer to this question would support for my mechanism.
answered 6 hours ago
Mathew MahindaratneMathew Mahindaratne
8,2991131
$endgroup$
1
$begingroup$
So the answer seems to be "No". Fair enough.
$endgroup$
– Oscar Lanzi
3 hours ago
add a comment |
$begingroup$
I don't think it is necessary to consider a mechanism with a nonclassical carbocation. It would undergo normal rearrangement with a 1,2-methide shift within the same ring. See the mechanism I posted in previous question you were directing to:
Answer to this question would support for my mechanism.
answered 6 hours ago
Mathew MahindaratneMathew Mahindaratne
8,2991131
$endgroup$
I don't think it is necessary to consider a mechanism with a nonclassical carbocation. It would undergo normal rearrangement with a 1,2-methide shift within the same ring. See the mechanism I posted in previous question you were directing to:
Answer to this question would support for my mechanism.
answered 6 hours ago
Mathew MahindaratneMathew Mahindaratne
8,2991131
edited 5 hours ago
answered 6 hours ago
Mathew MahindaratneMathew Mahindaratne
8,2991131
answered 6 hours ago
Mathew MahindaratneMathew Mahindaratne
8,2991131
answered 6 hours ago
Mathew MahindaratneMathew Mahindaratne
8,2991131
8,2991131
1
$begingroup$
So the answer seems to be "No". Fair enough.
$endgroup$
– Oscar Lanzi
3 hours ago
add a comment |
1
$begingroup$
So the answer seems to be "No". Fair enough.
$endgroup$
– Oscar Lanzi
3 hours ago
1
1
$begingroup$
So the answer seems to be "No". Fair enough.
$endgroup$
– Oscar Lanzi
3 hours ago
$begingroup$
So the answer seems to be "No". Fair enough.
$endgroup$
– Oscar Lanzi
3 hours ago
add a comment |
$begingroup$
While there are examples of 1,2-methide shifts, this question has an uncanny resemblance to the dienone-phenol rearrangement whose mechanism was first elucidated by Woodward and Singh in 1950. Dienone 1 under acidic conditions undergoes rearrangement to phenol 6 and not, based on earlier speculation, to phenol 4. The direct 1,2-methide shift (2b --> 3) does not occur but rather the reaction proceeds through the spiro carbocation 5. continued
Applying this approach to the carbocation 7 generated from the alcohol in this question, spiro carbocation 8 forms the predicted tetrahydronaphthalene 10. One way to distinguish between the two mechanisms is via a labeling experiment. All of the carbon label in 7 will retain its location as the red star in 10 if the 1,2-methyl shift mechanism applies. The spiro mechanism will partition the label ~50:50 between the two ring benzylic carbons. For related studies, see reference 2.
1) R. B. Woodward and T. Singh, J. Am. Chem. Soc., 1950, 72, 494.
2) A. J. Waring, J. H. Zaidi and J. W. Pilkington, J. Chem. Soc, Perkin Transactions I, 1981, 1454.
answered 2 hours ago
user55119user55119
4,51711242
$endgroup$
add a comment |
$begingroup$
While there are examples of 1,2-methide shifts, this question has an uncanny resemblance to the dienone-phenol rearrangement whose mechanism was first elucidated by Woodward and Singh in 1950. Dienone 1 under acidic conditions undergoes rearrangement to phenol 6 and not, based on earlier speculation, to phenol 4. The direct 1,2-methide shift (2b --> 3) does not occur but rather the reaction proceeds through the spiro carbocation 5. continued
Applying this approach to the carbocation 7 generated from the alcohol in this question, spiro carbocation 8 forms the predicted tetrahydronaphthalene 10. One way to distinguish between the two mechanisms is via a labeling experiment. All of the carbon label in 7 will retain its location as the red star in 10 if the 1,2-methyl shift mechanism applies. The spiro mechanism will partition the label ~50:50 between the two ring benzylic carbons. For related studies, see reference 2.
1) R. B. Woodward and T. Singh, J. Am. Chem. Soc., 1950, 72, 494.
2) A. J. Waring, J. H. Zaidi and J. W. Pilkington, J. Chem. Soc, Perkin Transactions I, 1981, 1454.
answered 2 hours ago
user55119user55119
4,51711242
$endgroup$
add a comment |
$begingroup$
While there are examples of 1,2-methide shifts, this question has an uncanny resemblance to the dienone-phenol rearrangement whose mechanism was first elucidated by Woodward and Singh in 1950. Dienone 1 under acidic conditions undergoes rearrangement to phenol 6 and not, based on earlier speculation, to phenol 4. The direct 1,2-methide shift (2b --> 3) does not occur but rather the reaction proceeds through the spiro carbocation 5. continued
Applying this approach to the carbocation 7 generated from the alcohol in this question, spiro carbocation 8 forms the predicted tetrahydronaphthalene 10. One way to distinguish between the two mechanisms is via a labeling experiment. All of the carbon label in 7 will retain its location as the red star in 10 if the 1,2-methyl shift mechanism applies. The spiro mechanism will partition the label ~50:50 between the two ring benzylic carbons. For related studies, see reference 2.
1) R. B. Woodward and T. Singh, J. Am. Chem. Soc., 1950, 72, 494.
2) A. J. Waring, J. H. Zaidi and J. W. Pilkington, J. Chem. Soc, Perkin Transactions I, 1981, 1454.
answered 2 hours ago
user55119user55119
4,51711242
$endgroup$
While there are examples of 1,2-methide shifts, this question has an uncanny resemblance to the dienone-phenol rearrangement whose mechanism was first elucidated by Woodward and Singh in 1950. Dienone 1 under acidic conditions undergoes rearrangement to phenol 6 and not, based on earlier speculation, to phenol 4. The direct 1,2-methide shift (2b --> 3) does not occur but rather the reaction proceeds through the spiro carbocation 5. continued
Applying this approach to the carbocation 7 generated from the alcohol in this question, spiro carbocation 8 forms the predicted tetrahydronaphthalene 10. One way to distinguish between the two mechanisms is via a labeling experiment. All of the carbon label in 7 will retain its location as the red star in 10 if the 1,2-methyl shift mechanism applies. The spiro mechanism will partition the label ~50:50 between the two ring benzylic carbons. For related studies, see reference 2.
1) R. B. Woodward and T. Singh, J. Am. Chem. Soc., 1950, 72, 494.
2) A. J. Waring, J. H. Zaidi and J. W. Pilkington, J. Chem. Soc, Perkin Transactions I, 1981, 1454.
answered 2 hours ago
user55119user55119
4,51711242
answered 2 hours ago
user55119user55119
4,51711242
answered 2 hours ago
user55119user55119
4,51711242
answered 2 hours ago
user55119user55119
4,51711242
4,51711242
add a comment |
add a comment |
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$begingroup$
Thanks for getting the name. IUPAC convention confuses me more than actual chemistry!
$endgroup$
– Oscar Lanzi
3 hours ago