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Hydrocarbons question

2019 · 9 Apr · Shift 1 · Q18
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Hydrocarbons question

2019 · 9 Apr · Shift 1 · Q18

JEE MainChemistryHydrocarbonsMCQ+4 / −1
The major product of the following reaction is : JEE Main 2019 (Online) 9th April Morning Slot Chemistry - Hydrocarbons Question 114 English
  1. A
    CH3CD2CH(Cl)(I)CH_3CD_2CH(Cl)(I)CH3​CD2​CH(Cl)(I)
  2. B
    CH3CD(Cl)CHD(I)CH_3CD(Cl)CHD(I)CH3​CD(Cl)CHD(I)
  3. C
    CH3C(I)(Cl)CHD2CH_3C(I)(Cl)CHD_2CH3​C(I)(Cl)CHD2​
  4. D
    CH3CD(I)CHD(Cl)CH_3CD(I)CHD(Cl)CH3​CD(I)CHD(Cl)
View written solutionFree

Correct answer: NONE OF THE GIVEN OPTIONS IS CORRECT; THE MAJOR PRODUCT SHOULD BE $CH_3CD(CL)CHD_2(I)$, WITH $CL$ ON THE MORE SUBSTITUTED CARBON AND $I$ ON THE LESS SUBSTITUTED CARBON.

  1. Identify the reaction type

The options indicate addition of III and ClClCl across a deuterated alkene. This corresponds to addition of iodine monochloride, IClIClICl, to an alkene.

In IClIClICl, chlorine is more electronegative, so the bond is polarized as:

Iδ+−Clδ−I^{\delta+}-Cl^{\delta-}Iδ+−Clδ−

Thus, the electrophile is effectively I+I^+I+.


  1. Determine the alkene from the products

All options have the carbon skeleton:

CH3−C−CCH_3- C - CCH3​−C−C

with two deuteriums distributed over the double-bond carbons. So the alkene must be:

CH3CD=CD2CH_3CD=CD_2CH3​CD=CD2​

Now we add IClIClICl across this double bond.


  1. Mechanism of addition of IClIClICl to alkene

Addition proceeds through formation of an iodonium ion first, because I+I^+I+ attacks the double bond.

Then Cl−Cl^-Cl− opens the halonium ion.

For such additions, the orientation is governed by the carbocation-like character in the bridged intermediate: the nucleophile Cl−Cl^-Cl− attacks the more substituted carbon.

So effectively:

  • III goes first to the alkene,
  • ClClCl finally ends up on the more substituted carbon.

In the alkene

CH3CD=CD2CH_3CD=CD_2CH3​CD=CD2​

  • Left alkene carbon (CH3CD=CH_3CD=CH3​CD=) is more substituted.
  • Right alkene carbon (=CD2=CD_2=CD2​) is less substituted.

Therefore:

  • ClClCl goes to the left carbon,
  • III goes to the right carbon.

So the product should be:

CH3C(Cl)D−CHD2(I)CH_3C(Cl)D-CHD_2(I)CH3​C(Cl)D−CHD2​(I)

which can be written as:

CH3CD(Cl)CHD2(I)CH_3CD(Cl)CHD_2(I)CH3​CD(Cl)CHD2​(I)

Matching the options, this is Option B? Let us check carefully.


  1. Check each option carefully

Starting alkene: CH3CD=CD2CH_3CD=CD_2CH3​CD=CD2​

After addition, each double-bond carbon gains one new substituent:

  • Left carbon already has CH3CH_3CH3​ and DDD, so it gets either ClClCl or III and no extra H/D.
  • Right carbon already has D2D_2D2​, so it gets either ClClCl or III.

Thus the valid connectivity after addition must look like one of these two regioisomers:

CH3C(D)(Cl)−C(D2)(I)CH_3C(D)(Cl)-C(D_2)(I)CH3​C(D)(Cl)−C(D2​)(I) nor CH3C(D)(I)−C(D2)(Cl)CH_3C(D)(I)-C(D_2)(Cl)CH3​C(D)(I)−C(D2​)(Cl)

Now inspect options:

  • A: CH3CD2CH(Cl)(I)CH_3CD_2CH(Cl)(I)CH3​CD2​CH(Cl)(I)
    Impossible: left carbon has become CD2CD_2CD2​, which would mean deuterium count changed incorrectly.

  • B: CH3CD(Cl)CHD(I)CH_3CD(Cl)CHD(I)CH3​CD(Cl)CHD(I)
    This has one DDD on each carbon after addition, so total deuterium count is only 2, whereas alkene had 3 deuteriums. Impossible.

  • C: CH3C(I)(Cl)CHD2CH_3C(I)(Cl)CHD_2CH3​C(I)(Cl)CHD2​
    This puts both III and ClClCl on the same carbon. Not possible for simple addition across a double bond.

  • D: CH3CD(I)CHD(Cl)CH_3CD(I)CHD(Cl)CH3​CD(I)CHD(Cl)
    Again only 2 deuteriums total, so impossible.


  1. Conclusion from chemical reasoning

None of the options exactly matches the chemically correct product expected from addition of IClIClICl to CH3CD=CD2CH_3CD=CD_2CH3​CD=CD2​.

The correct major product should be:

CH3CD(Cl)−CD2(I)CH_3CD(Cl)-CD_2(I)CH3​CD(Cl)−CD2​(I)

or equivalently

CH3C(D)(Cl)CHD2(I)CH_3C(D)(Cl)CHD_2(I)CH3​C(D)(Cl)CHD2​(I)

Since this is not among the given options, the stored answer C is chemically inconsistent.


  1. Comparison with stored answer

Stored correct answer: C

But option C is not a valid addition product, since it places both halogens on the same carbon.

Therefore, I disagree with the stored answer.

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