Organic Chemistry

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4 Apr 2012 22:32:16 IST
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can there be rearrangement when we add water to alkynes....depending on stability???can u explain wid plausible mechanism???hlp urgent



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Blazing goIITian

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4 Apr 2012 22:34:05 IST
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in presence of dilute h2so4
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Scorching goIITian

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4 Apr 2012 22:34:51 IST
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yes..explain wd mech./

Blazing goIITian

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4 Apr 2012 22:37:25 IST
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sorry mechanics cant be displayed and yes there can be reaarrangement but hen two moles of water is added

Blazing goIITian

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4 Apr 2012 22:38:01 IST
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sorry mechanics cant be displayed and yes there can be reaarrangement bcoz allylic carbocation is more stable than simple one
ronnie's Avatar

Scorching goIITian

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4 Apr 2012 22:42:23 IST
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i need mechanism..since iit q.2011 didnt considr rearrangemnt..

Blazing goIITian

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4 Apr 2012 22:44:06 IST
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question no. and paper.....
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Scorching goIITian

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4 Apr 2012 22:54:45 IST
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PAPER 1.PARA Q.

Blazing goIITian

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4 Apr 2012 22:58:19 IST
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oh yeah buttttttttttt
Madhusudan Chavan's Avatar

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6 Apr 2012 07:08:47 IST
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 I am trying to paste the mechanism, hope it appears properly

As with alkenes, the addition of water to alkynes requires a strong acid, usually sulfuric acid, and is facilitated by mercuric sulfate. However, unlike the additions to double bonds which give alcohol products, addition of water to alkynes gives ketone products ( except for acetylene which yields acetaldehyde ). The explanation for this deviation lies in enol-keto tautomerization, illustrated by the following equation. The initial product from the addition of water to an alkyne is an enol (a compound having a hydroxyl substituent attached to a double-bond), and this immediately rearranges to the more stable keto tautomer.

http://www2.chemistry.msu.edu/faculty/reusch/VirtTxtJml/Images2/ketentau.gif

Tautomers are defined as rapidly interconverted constitutional isomers, usually distinguished by a different bonding location for a labile hydrogen atom (colored red here) and a differently located double bond. The equilibrium between tautomers is not only rapid under normal conditions, but it often strongly favors one of the isomers ( acetone, for example, is 99.999% keto tautomer ). Even in such one-sided equilibria, evidence for the presence of the minor tautomer comes from the chemical behavior of the compound. Tautomeric equilibria are catalyzed by traces of acids or bases that are generally present in most chemical samples. The three examples shown below illustrate these reactions for different substitutions of the triple-bond. The tautomerization step is indicated by a red arrow. For terminal alkynes the addition of water follows the Markovnikov rule, as in the second example below, and the final product ia a methyl ketone ( except for acetylene, shown in the first example ). For internal alkynes ( the triple-bond is within a longer chain ) the addition of water is not regioselective. If the triple-bond is not symmetrically located ( i.e. if R & R' in the third equation are not the same ) two isomeric ketones will be formed.

HC≡CH   +   H2O   +   HgSO4 & H2SO4   ——>  [ H2C=CHOH ]   ——>   H3C-CH=O

RC≡CH   +   H2O   +   HgSO4 & H2SO4   ——>  [ RC(OH)=CH2 ]   ——>   RC(=O)CH3

RC≡CR'   +   H2O   +   HgSO4 & H2SO4   ——>  [ RHC=C(OH)R'   +   RC(OH)=CHR' ]   ——>   RCH2-C(=O)R'   +   RC(=O)-CH2R'

 


 

Hydration. The addition of the elements of water across the triple bond of an alkyne leads to the formation of aldehydes and ketones. Water addition to terminal alkynes leads to the generation of aldehydes, while nonterminal alkynes and water generate ketones.

These products are produced by rearrangement of an unstable enol (vinyl alcohol) intermediate. The term “enol” comes from the en in “alkene” and ol in “alcohol,” reflecting that one of the carbon atoms in vinyl alcohol has both a double bond (alkene) and an OH group (alcohol) attached to it. A vinyl group is

 

http://media.wiley.com/Lux/18/22318.nst020.gif

 

and a vinyl alcohol is

 

http://media.wiley.com/Lux/19/22319.nst021.gif

 

Water adds across the triple bond of an alkyne via a carbocation mechanism. Dilute mineral acid and mercury(II) ions are needed for the reaction to occur.

 

http://media.wiley.com/Lux/20/22320.nst022.gif

 

The first step of the mechanism is an acid-base reaction between the mercury(II) ion (Hg2+) and the π system of the alkyne to form a π complex.

 

http://media.wiley.com/Lux/21/22321.nst023.gif

 

The π complex is converted into a single bond between one or the other of the carbons of the triple bond and the mercury (II) ion, with the resulting generation of a carbocation.

 

http://media.wiley.com/Lux/22/22322.nst024.gif

 

A molecule of water is attracted to the carbocation to form an oxonium ion.

 

http://media.wiley.com/Lux/23/22323.nst025.gif

 

The oxonium ion loses a proton to stabilize itself.

 

http://media.wiley.com/Lux/24/22324.nst026.gif

 

The vinyl alcohol precursor that results is converted into vinyl alcohol (enol) by reaction with a hydronium ion (H3O+).

 

http://media.wiley.com/Lux/25/22325.nst027.gif

 

Vinyl alcohols (enols) are unstable intermediates, and they undergo rapid isomerization to form ketones. Such isomerization is called keto-enol tautomerism.

 

http://media.wiley.com/Lux/26/22326.nst028.gif

 

In a similar fashion, the less-stable intermediate generates an aldehyde.

 

http://media.wiley.com/Lux/27/22327.nst029.gif

 

 

Madhusudan Chavan's Avatar

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6 Apr 2012 07:10:34 IST
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 Please refer to following for the mechanism

www.cliffsnotes.com/.../Alkynes-Addition-Reactions.topicArticleId-2...

www2.chemistry.msu.edu/faculty/reusch/VirtTxtJml/addyne1.htm


Hot goIITian

Joined: 4 Apr 2012
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6 Apr 2012 09:04:25 IST
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Actually rearrangement doesn't occure..........its answer is ' ALL TERMINAL ALKYNES GIVE KETONE AS A FINAL PRODUCT AND ALL NON-TERMINAL ALKYNES GIVE ALDEHYDE AS A FINAL PRODUCT'..................................................................................................................



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