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Chemistry Forums for Students => Organic Chemistry Forum => Topic started by: lord farquaad on January 24, 2022, 10:16:55 AM

Title: Does the substitution of the nucleophile matter during an SN2 reaction?
Post by: lord farquaad on January 24, 2022, 10:16:55 AM
SN2 is likely to occur when the alkyl halide has primary substitution. But will SN2 still occur if the nucleophile has tertiary substitution? I was surprised that the explanation for this reaction (attached) was that it occurred through SN2 mechanism. I thought the fact that O is so sterically hindered would prevent SN2.
Title: Re: Does the substitution of the nucleophile matter during an SN2 reaction?
Post by: Babcock_Hall on January 24, 2022, 10:47:39 AM
I remember looking up the behavior of tertiary-butoxide as a nucleophile one time.  It is a good nucleophile against iodomethane.  Do you think that there could be a reaction competing with the SN2 process?
Title: Re: Does the substitution of the nucleophile matter during an SN2 reaction?
Post by: rolnor on January 24, 2022, 03:49:51 PM
Sn1 goes via a carbocation, the primary halide can hardly not form this. What will happen with a bulky nucleophile is that the reaction is slow or does not occur at all or you get elimination.
Title: Re: Does the substitution of the nucleophile matter during an SN2 reaction?
Post by: Babcock_Hall on January 24, 2022, 05:04:29 PM
When iodomethane is the electrophile and the solvent is DMF, the rate constant for tertiary-butoxide is about twice that of ethoxide (Daley and Daley, p. 537).  Unfortunately, I don't have this book, and I don't know what the rates are with other alkyl halides.  The text on this page implies that tert-butoxide reacts slowly with other alkyl halides.  There was a thread here that mentioned this in 2016.
https://www.chemicalforums.com/index.php?topic=88451.0
Title: Re: Does the substitution of the nucleophile matter during an SN2 reaction?
Post by: rolnor on January 24, 2022, 11:59:43 PM
Iodomethane is less sensitive to this problem, its so small. tert-butoxide is a stronger base and probably a more powerfull nucleophile then ethoxide. Sodium ethoxide has pka 15,5 potassium tert-butoxide has 17.