(Sni and NGP) for 2ND SEMESTER STUDENTS

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ADDITIONAL MODULE OF SUBSTITUTION REACTION (SNi AND NGP) FOR 2ND SEMESTER STUDENTS Part A: SNi Substitution Reactions Dr. Subhra Mishra Associate Professor, Deptt. Of Chemistry, Kharagpur College (Nucleophilic Substitution Internal) The reaction follows the second order rate equation; Rate = k2 [Substrate] [SOCl2] SNi Two proposed mechanism: 1. Concerted 2. Through the formation of intimate ion pair (In intimate ion pair, an ion is completely shielded by the counter ion. There are no solvent molecule between two ions) The intimate ion pair within a solvent cage is further attacked by Cl- is likely to occur from the same side of the departing gr. ie. with retention of configuration SNi reaction in presence of different solvents: The HCl formed from ROH and SOCl2 is converted py, into + - - C5H5NH Cl and Cl beeing a Nu- attack form the backside The SNi reaction in presence of pyridine or dioxane occurs through the inversion of configuration of the substrate SNi reaction for bridgehead Molecules:?? In case of such rigid molecule, formation of such non classical carbocation formation is unusual, but as ion pair formation does not involve formal carbocation, replacement of hydroxyl group can easily occur. Part B: Neighboughing Group Participation (NGP) NGP NGP NGP NGP NGP NGP NGP NGP NGP NGP NGP Some additional problems…………….. 1. Example of π bond participation. 2. Example of bond participation Solve the following problems: 4 1. EtSCH2CH2Cl is found to undergo hydrolysis 10 times faster than EtOCH2CH2Cl-Expalin 2. Base hydrolysis of 1,2 chlorohydrin is found to yield the 1,2 diol with retention of configuration- Explain 3. Give evidence in favor of concerted mechanism of SNi substitution reaction. .

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Recent Advances in the Direct Nucleophilic Substitution of Allylic
SHORT REVIEW ▌25 Recentshort review Advances in the Direct Nucleophilic Substitution of Allylic Alcohols through SN1-Type Reactions AlejandroSN1 Reactions of Allylic Alcohols Baeza,* Carmen Nájera* Departamento de Química Orgánica and Instituto de Síntesis Orgánica, University of Alicante, Apdo.99, 03080 Alicante, Spain Fax +34(965)903549; E-mail: [email protected]; E-mail: [email protected] Received: 03.10.2013; Accepted after revision: 06.11.2013 Abstract: Direct nucleophilic substitution reactions of allylic alco- hols are environmentally friendly, since they generate only water as a byproduct, allowing access to new allylic compounds. This reac- tion has, thus, attracted the interest of the chemical community and several strategies have been developed for its successful accom- plishment. This review gathers the latest advances in this methodol- ogy involving SN1-type reactions. 1 Introduction 2SN1-Type Direct Nucleophilic Substitution Reactions of Allylic Alcohols 2.1 Lewis Acids as Catalysts Alejandro Baeza was born in Alicante (Spain) in 1979. He studied 2.2 Brønsted Acids as Catalysts chemistry at the University of Alicante and he received his M.Sc. (2003) and Ph. D. degrees (2006) from here under the supervision of 2.3 Other Promoters Prof. José Miguel Sansano and Prof. Carmen Nájera. He was a post- 3 Conclusions and Outlook doctoral researcher in Prof. Pfaltz’s research group (2007–2010). In 2010 he returned to Alicante and joined the research group of Prof. Key words: S 1 reaction, allylic substitution, carbocations, allylic N Carmen Nájera. His main research interests focus on the development alcohols, green chemistry of new environmentally friendly methodologies, especially in asym- metric synthesis.
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