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This document discusses different mechanisms for nucleophilic substitution reactions. It explains that nucleophilic substitution of alcohols with hydrogen halides can produce rearranged products through carbocation intermediates, but reactions with sulfur or phosphorus halides follow an SNi mechanism without rearrangement. The SNi mechanism involves the nucleophile attacking from the same side as the leaving group to give retention of configuration. Neighboring group participation allows some SN2 reactions to proceed with retention of configuration through two inversion steps. The document also describes an E1CB mechanism where a conjugate base is generated through proton abstraction prior to elimination of the leaving group.
This document discusses different mechanisms for nucleophilic substitution reactions. It explains that nucleophilic substitution of alcohols with hydrogen halides can produce rearranged products through carbocation intermediates, but reactions with sulfur or phosphorus halides follow an SNi mechanism without rearrangement. The SNi mechanism involves the nucleophile attacking from the same side as the leaving group to give retention of configuration. Neighboring group participation allows some SN2 reactions to proceed with retention of configuration through two inversion steps. The document also describes an E1CB mechanism where a conjugate base is generated through proton abstraction prior to elimination of the leaving group.
This document discusses different mechanisms for nucleophilic substitution reactions. It explains that nucleophilic substitution of alcohols with hydrogen halides can produce rearranged products through carbocation intermediates, but reactions with sulfur or phosphorus halides follow an SNi mechanism without rearrangement. The SNi mechanism involves the nucleophile attacking from the same side as the leaving group to give retention of configuration. Neighboring group participation allows some SN2 reactions to proceed with retention of configuration through two inversion steps. The document also describes an E1CB mechanism where a conjugate base is generated through proton abstraction prior to elimination of the leaving group.
Nucleophilic substitution of alcohol with HX gives
haloalkane but there is possibilities for the formation of rearranged products especially when there is formation of carbocations.
However when sulphur or phosphorous halides are used , no rearrangement product obtained. It follows Sni mechanism (Substitution Nucleophilic Internal) Eg:
R-OH + SOCl2 R-Cl + so2 + HCl MECHANISM FIRST STEP: The lone pair of oxygen attacks electrophilic centre of SO2Cl2 (S)gives positive charge In oxygen and negative on other to form an unstable ion pair which eliminates a molecule of HCl to form Alkyl chloro sulphite intermediate (similar to SN1) SECOND STEP Internal attack of the nucleophile Chlorin to the electrophilic Carbon from the same side , breaking C-O bond with the elimination of SO2 molecule Here Nucleophile attacks from the same side of the leaving group which leads to retention of configuration Eg NIGHBOURING GROUP PARTICIPATION In some cases the rate of SN2 reactions is found to be extremely high and the Product is obtained with the retention of configuration. These reactions follows Nighbouring group mechanism Here nighbouring group acts as nucleophile.. Ie one of the nucleophile is a part of the same molecule and is located at the C atom or farther from the leaving group
As it involves two steps with Sn2 mechanism two inversions leads to retention of configuration In the first step attack of neighboring group at the carbon from the backside forming an unstable intermediate with inversion of configuration ( SN2 reaction ) In the second stage nucleophilic attack takes place to form the product with inversion of configuration ( Another SN2 reaction) ie two SN2 reactions with inversion of configuration . Final product with retention of configuration Eg:: First step Second step L-2- BROMOPROPIONATE L-2- METHOXY PROPIONATE FEATURES
1)High reaction rate compared to SN2
2)Followsfirst order keinetics (substrate only)
3)Retention as a result of two inversion
4)Also called Anchimeric assistance E1CB MECHANISM (UNIMOLECULAR MECHANISM FROM A CONJUGATE BASE) In E1CB mechanism a proton is initially abstracted to generate conjugate base at equilibrium which then loses L- giving elimination products in therate determing step
As the proton has to be removed from a carbon from a neutral species ( a difficult job) A strong base is needed for E1CB reaction as in E2 reaction. More over increase in strength of base and concentration of base increase the rate of E1CB reaction If more than one beta hydrogen more acidic hydrogen is removed Better the leaving group, better will be the rate of E1CB reaction ( if E1CB is operating) Because rds involve the leaving group otherwise if the leaving group is so good It will leave before the anion is formed leading to E2 mechanism E1CB mechanism operates when the abstraction of proton is very easy ( removal from a highly electronegative atom)and the conjugate base is resonance stabilised) E1CB mechanism also operates when the expulsion of leaving group is difficult ( Leaving group is bad like F-,-OH-,RO- etc or if leaving group has partial double bond due to resonance) Eg Dehydrohaloganation of geminal halohydrin because H+ is removed from highly electronegative oxygen 2 Dehydrohalogenation of carbonyl compounds because resultant carbanion is resonance stabilised If the leaving group is a better leaving group, E1CB reaction will takes place But if the leaving group is very good E2 reaction will takesplace 3- Dehydroflurination of because fluoride is a bad leaving group 4 Dehydrohalogenation when halogen has partial double bond due to resonance in vinyl halide and aryl halides 5 Dehydration in basic medium