Chapter 15 Substitutions at the Carbonyl Group

Chapter 15 Substitutions at the Carbonyl Group -...

Info iconThis preview shows pages 1–8. Sign up to view the full content.

View Full Document Right Arrow Icon
1 Chapter 15 Substitutions at the Carbonyl                   Group 15.2 Nucleophilic substitution at a carbonyl carbon + Y R-C-B O Y O R-C-B + B O R-C-Y O Y = Cl, OH, OR, NH 2 , NHR, NRR', OCR O R-C-B - HY OH R-C-B Y Y :OH R-C-B :B R-C-Y OH + H R-C-Y O + + + Y General expressions: basic condition acidic condition
Background image of page 1

Info iconThis preview has intentionally blurred sections. Sign up to view the full version.

View Full DocumentRight Arrow Icon
2 The order of basicity of leaving groups: Weak: Cl - < RCOO - < - OH < - OR < - NH 2 strong The order of reactivity towards nucleophilic substitution: 15.3 Synthesis of acyl chlorides stability increase reactivity increase R-C-NH 2 O R-C-OR O > R-C-OH O > O R-C-O-C-R O > > O R-C-Cl R-C-Cl O - POCl 3 ,- HCl PCl 5 O R-C-OH PCl 3 , SOCl 2 (thionyl chloride,
Background image of page 2
3 The reactions of acyl chlorides: R-C-R' OH R' H 3 O R' OMgCl R-C-R' R'MgCl O R-C-R' + HCl + HCl + R'Cu + LiCl + R'NH 3 Cl + NH 4 Cl + HCl -MgCl 2 R'MgCl R' 2 CuLi NH 2 R' NH 3 R'OH H 2 O R-C-R' O R'-C-OH O O R-C-O-C-R' O O R-C-NHR' O R-C-NH 2 O R-C-OR' O R-C-OH O R-C-Cl +
Background image of page 3

Info iconThis preview has intentionally blurred sections. Sign up to view the full version.

View Full DocumentRight Arrow Icon
4 15.4 Synthesis of carboxylic acid anhydrides (RCO) 2 O + 2CH 3 COOH (RCO) 2 O + H 2 O (CH 3 CO) 2 O P 2 O 5 2RCOOH Cl H N + O O RC-O-CR' N + O RCOOH + R'-C-Cl + O O O C C H H C C -H 2 O COOH C C H H COOH HOOC COOH H H C C fumaric acid maleic acid - NaCl RC-O-CR' O O RCOONa + R'-C-Cl O
Background image of page 4
5 15.5 Synthesis and reactions of esters a. Synthesis of esters i. From carboxylic acids (esterification, 5 ) O O C C NH 2 OH NH C C O O - NH 3 , - H 2 O H 3 O NH 4 NH 2 C C O O 2NH 3 O O O C C O + + H RCOOR' + H 2 O RCOOH + R'OH + 1 2 , amidic acid 5 imide 5 water segregator 5 (p 661)
Background image of page 5

Info iconThis preview has intentionally blurred sections. Sign up to view the full version.

View Full DocumentRight Arrow Icon
6 The reactivity of esterification: for alcohols: CH 3 OH > 1°ROH > 2 °ROH > 3 °ROH for acids: HCOOH > CH 3 COOH, RCH 2 COOH > R 2 CHCOOH > R 3 CCOOH model B model A RC-O-H + HO-R' O + H-OR' O RC-OH + H 2 O O RC-OCH 3 H + HOCH 3 RC-OH O 18 18 + + H 2 O CH 2 CH 3 H CH 3 s RC-O-C O H CH 2 CH 3 H CH 3 s + HO-C O RC-OH + configuration retention
Background image of page 6
O O R CH C (CH 2 ) n H O OH RHC(CH 2 ) n -C-OH + n = 2 γ -lactone n = 3 δ -lactone Cl H + R-C-O-C-C O C C N R-C-Cl O + HO-C-C
Background image of page 7

Info iconThis preview has intentionally blurred sections. Sign up to view the full version.

View Full DocumentRight Arrow Icon
Image of page 8
This is the end of the preview. Sign up to access the rest of the document.

Page1 / 31

Chapter 15 Substitutions at the Carbonyl Group -...

This preview shows document pages 1 - 8. Sign up to view the full document.

View Full Document Right Arrow Icon
Ask a homework question - tutors are online