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Chapter 8 Nucleophilic Substitution. 8.1 Functional Group Transformation By Nucleophilic Substitution. –. –. : X. Y :. Nucleophilic Substitution. +. R. +. Y. R. X. nucleophile is a Lewis base (electron-pair donor) often negatively charged and used as Na + or K + salt
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8.1Functional Group Transformation By Nucleophilic Substitution
– – : X Y : Nucleophilic Substitution + R + Y R X • nucleophile is a Lewis base (electron-pair donor) • often negatively charged and used as Na+ or K+ salt • substrate is usually an alkylhalide
X C C Nucleophilic Substitution Substrate cannot be an a vinylic halide or an aryl halide, except under certain conditions to be discussed in Chapter 23. X
– .. R X R' O: .. .. – + R' R : X O .. Table 8.1 Examples of Nucleophilic Substitution Alkoxide ion as the nucleophile + gives an ether
Example (CH3)2CHCH2ONa + CH3CH2Br Isobutyl alcohol (CH3)2CHCH2OCH2CH3 + NaBr Ethyl isobutyl ether (66%)
O R X O Table 8.1 Examples of Nucleophilic Substitution Carboxylate ion as the nucleophile – .. + R'C O: .. gives an ester .. – + R'C R : X O ..
O O Example + CH3(CH2)16C OK CH3CH2I acetone, water + CH3(CH2)16C KI O CH2CH3 Ethyl octadecanoate (95%)
– .. R X H S: .. .. – + H R : X S .. Table 8.1 Examples of Nucleophilic Substitution Hydrogen sulfide ion as the nucleophile + gives a thiol
Example KSH + CH3CH(CH2)6CH3 Br ethanol, water + KBr CH3CH(CH2)6CH3 SH 2-Nonanethiol (74%)
: : N R X C : N C Table 8.1 Examples of Nucleophilic Substitution Cyanide ion as the nucleophile – + gives a nitrile – + R : X
Br CN Example NaCN + DMSO + NaCN Cyclopentyl cyanide (70%)
+ – – : : N N N R X .. .. – : N N N .. .. Table 8.1 Examples of Nucleophilic Substitution Azide ion as the nucleophile + gives an alkyl azide + – + R : X
Example NaN3 + CH3CH2CH2CH2CH2I 2-Propanol-water CH3CH2CH2CH2CH2N3 + NaI Pentyl azide (52%)
.. : : I R X .. .. : I .. Table 8.1 Examples of Nucleophilic Substitution Iodide ion as the nucleophile – + gives an alkyl iodide – + R : X
+ NaI CH3CHCH3 Br Example acetone + NaBr CH3CHCH3 NaI is soluble in acetone; NaCl and NaBr are not soluble in acetone. I 63%
Generalization • Reactivity of halide leaving groups in nucleophilic substitution is the same as for elimination. most reactive RI RBr RCl RF least reactive
Problem 8.2 A single organic product was obtained when 1-bromo-3-chloropropane was allowed to react with one molar equivalent of sodium cyanide in aqueous ethanol. What was this product? • Br is a better leaving group than Cl BrCH2CH2CH2Cl + NaCN
: N C CH2CH2CH2Cl + NaBr Problem 8.2 A single organic product was obtained when 1-bromo-3-chloropropane was allowed to react with one molar equivalent of sodium cyanide in aqueous ethanol. What was this product? BrCH2CH2CH2Cl + NaCN