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AMIDE NITROGEN continued CYCLIZATION:

Imide: R-CO-NH-CO-R’
SYNTHESIS OF A CYCLIC
Nomenclature: O COMPOUND
• Example: Me-CO-NH2, acetamide R Synthesis:
C Synthesis:
• Cyclic amide (lactam): N of amide R • Dehydration, amide + carboxylic acid
N R
forms ring with β, γ or δ carbon; • Diels-Alder: diene + dienophile + heat => adduct
Oxime: >C=NOH
• β forms 4 membered ring; γ forms a 5 membered ring, Synthesis:
δ form a 6 membered ring. • aldehyde/ketone + hydroxylamine +
• Observed in amino acids Reaction:
Synthesis: • oxime to 1º amine (Na, EtOH) Diene Dienophile Adduct
• Nitrile hydrolysis (R-CN + H2O, conc. H2SO4) • Freund-Gustavson: 3-membered ring from 1,3
• Acyl chloride + 1º/2º amine or ammonia dihalide (EtOH, Zn, heat)
• Pyrolysis of ammonium salt + RCOOH
• Ammonolysis of ester: 1º or 2º amine + ester
ORGANIC POLYMER • [2,2] cycloaddition of alkenes giving cyclobutane
adduct (two alkenes, photochemical reaction)
• Polyamide => polypeptide => protein -M- M -M - M - M -
Reaction: Reaction of cyclic compound:
Monomers (M) bond to form a high molecular
• Retro-Diels-Alder: thermally decompose cycloalkene
• Reduce to amine (LiAlH4) weight compound.
• Reduce aromatic to symmetric 1,4 cycloalkene (Li or
• Hydrolyze to acid (H2O, H+ or OH-)
Factors which influence properties: chain length, Na, EtOH, Liq NH3) (Birch)
• Dehydrate to nitrile, RCN (P4O10, heat)
branching vs. linear, nature of the monomer, density, • Small ring is strained, may decompose to linear chain
• Hofmann Reaction: Form 1º amine (NaOBr)
interchain bonds, hydrophobic and hydrophilic • Epoxide ring opening reaction
• Grignard (R~MgX) to ketone, R-CO-R~ interactions.
• Form aldehyde and 2º amine (LiAlH2 (OEt)2) • Examples:
• Nucleophilic substitution; Form R-CO-Nu + amine • PE (polyethylene)
• PS (polystyrene)
METAL REACTION
• HDPE (high density polyethylene) Organometallic:
AMINO ACID • LDPE (low density polyethylene) • Carbon atom bonded to a metal atom
• PET (polyethylene teraphthalate) • Types of bonding:
CO2H H • ionic bond, Na,K; R--M+
Synthesis:
• partial covalent, Mg, Li; R electrophilic character
H 2N H R C CO2H • Free-radical synthesis: ethylene => PE;
• covalent, Pb, Sn, Hg; R-M
styrene => PS (radical initiation)
NH2 Grignard reagent:
R • Condensation: • Strong base gives R electrophilic character:
• HO-R-OH+HO-R’-OH => HO-R-R’-OH + H2O • Li + R-Br => R-Li
Properties:
• Example: ethylene glycol and teraphthalic acid => PET • RX + Mg => RMgX
• Basic (-NH2) and acidic (-COOH) functionality
Reaction: • ArX + Mg => ArMgX
• Chiral isomers
• Hydrolysis of polymer (reverse of condensation) Organoborane:
• Zwitterion: self-ionization of amino acid to produce • Boron hydride, BnHm
COO- and -NH3+ • Cross-link adjacent polymer chains or segments
example: diborane, B2H6
• Isoelectric point, pH which produces equal + and - • Synthesis:
charges • Hydroboration: Alkene + Boron hydride
SULFUR CHEMISTRY syn addition
Nomenclature: • Reaction:
• Common name based on “R” group; Sulphur Compounds • Organoborane => alcohol (H2O2/OH-)
examples: glycine (-H), alanine (-CH3) • Thiol: R-SH • R-B< => R-H (acetic acid; addition of H)
• Sulfide or Thioether: R-S-R’ Organolithium: R-Li
Synthesis: • Disulfide: R-S-S-R’ Synthesis:
• Gabriel synthesis: RCH2COOH + Br2, PCl3, NH3 • Thiol ester: R-CO-SR’ • Li + haloalkane (R-X or Ar-X) (cold, Et2O)
• Sulfoxide: R-S-OR’ Organomagnesium: RMgX or ArMgX
Reaction: • Grignard: RX + Mg (Et2O); R behaves as R-
• Sulfone: R-SO2-R’
• Lactam formation (cyclic amide) Organocopper: R-Cu
• Thiophenol: Ar-SH
• Polypeptide formation (peptide bond); • Thioketone: R-CS-R’ • Add R- to C=C of unsaturated carbonyl
dehydration: R-NH2 and HO-R’ moieties • Sulfonic acid: R-SO3H Organolead/mercury:
• Protein, amino acid polymer • Sulfinic Acid: R-SO2H • Stable compound, VOLATILE AND TOXIC
• Hydrogen sulfate: R-OSO3H • Tetraethyl lead (anti-knock agent in gasoline)

OTHER NITROGEN- ISBN-13: 978-142320285-1


ISBN-10: 142320285-6
COMPOUNDS Thiophene, Heterocyclic
sulphur compound
Nitrile: R-C≡N: S
example: H3C-CN; methane nitrile
Synthesis: Synthesis: CREDITS PRICE
• Thiol: From alkyl bromide/iodide (KOH, H2S) Author: Mark Jackson, PhD. U.S.$4.95
• Haloalkane + NaCN
Layout: Andre Brisson CAN.$7.50
• Aldehyde/ketone => cyanohydrin (CN-, H+) • Thiol: RCH2X + NaSH => RCH2SH (EtOH, heat) Note: Due to the condensed nature of this chart, use as a quick reference guide, not as
• Thiol ester: Acyl chloride + thiol a replacement for assigned course work. The reaction reagents are noted for illustrative
• Dehydrate amide (P4O10, heat) purposes only; this should not serve as guide for lab experiment procedures.
• Alkyl hydrogen sulfate (Alkene + cold conc. H2SO4)
Reaction: All rights reserved. No part of this publication may be reproduced or transmitted in any form, or by any means,
• Thiol: Alkene + H2S (H2SO4, heat) electronic or mechanical, including photocopy, recording, or any information storage and retrieval system,
without written permission from the publisher.
• Hydrolyze to carboxylic acid (acid, heat) (Markovnikoff addition) ©2001 BarCharts, Inc. 1106

• Hydrolyze to carboxylate (base, heat) • Thiol: Alkene+H2S (peroxide or UV) Customer Hotline # 1.800.230.9522
• Reduce to 1º amine (Raney Ni; LiAlH4) (Anti-Markovnikoff addition)
hundreds of titles at
• Form aldehyde (DIBAL-H (i-Bu)2AlH, H2O) Reaction: quickstudy.com
• Form ketone (Grignard reagent or R-Li, H+) • Form sulfide from thiol (NaOH, R’CH2X)
• Form disulfide from thiol (I2 or H2O2)
Imine: >C=N-R • Oxidize thiol to form sulfonic acid, RSO3H, (HNO3)
Synthesis: Aldehyde/ketone + 1º amine (H+) • Desulfurization of thiol to alkane (H2, Ni)
Reaction: Intermediate in amination of aldehyde/ketone • Sulfonate benzene (SO3, conc. H2SO4)
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