Index

A butan-2-ol 169 acetic acid 168–169 butan-2-one 169 acetic anhydride 167 t-butanol 169 acetone 166 iso-butanol 169 acetonitrile 167 t-butyl methyl ether 170 adsorption chromatography 38–40 air-sensitive substances see water- and C air-sensitive substances calcium chloride 161 alumina 39, 44, 45, 47 calcium hydride 161 drying agent 161 calcium oxide 162 amines 56 calcium sulphate 162 aminobenzene 167 CAplusSM 88 ammonia 167 carbon disulphide 170 aniline 167 carbon tetrachloride 170 anisole 168 carbon-13 compounds 143 Annual Reports in Organic Synthesis carbon-14 compounds 143 105 carboxylic acids 56 argon 130 carcinogens 14–16 assymetric synthesis and catalysis 138 CAS REGISTRYSM 88 azeotropes 35 CASREACT® 88 CHEMCATS 89 B Chemical Abstracts 75, 88 barium oxide 161 chemical shift 70 Beilstein test 156 CHEMLIST 89 benzene 168 chiral compounds, preparation of 138 biological exposure limits 15–16 chlorobenzene 171 bleeding and cuts 5–6 chloroform 171 boiling point chromatography azeotropes 35 adsorption 38–39 simple distillation 28 chromatogram development 40–41 variation with pressure 28 column 42–44 bumping 33 dimensions and adsorbant bunsen burner 2 quantities 45–48 burns 5 eluents butan-1-ol 168 classifi ed 39

Practical Organic Synthesis: A Student’s Guide R. Keese and M. P. Brändle © 2006 John Wiley & Sons, Ltd. 194 INDEX

chromatography (continued) search for properties 85–86 column chromatography 44–45 search for reactions 84–85 enantiomorphic purity types of search 77 determination 139 cryostatic slush baths 137 HPLC 51–54 crystallisation 20–23, 44, 130, 132 phases 37–39 dissolution 21–22 record sheet 48 drying 25 temperature dependence 40 fi ltration 22 theoretical plates 53–54 fractional 23–24 thick-layer 41 low temperature 136 thin-layer 40–41 melting point and purity 25 types classifi ed 37–38 nucleation 23 citation search 103–105 plan of procedure 20–21 Clausius-Clapeyron relationship 28 supersaturated solutions 23 cold bath 34 under inert gas 134 cold traps 34 cuts and bleeding 5–6 column chromatography 42–44 cyclohexane 171–172 eluents 44 estimating dimensions 45–47 D rapid (fl ash) 49–51 dangerous materials see hazardous record sheet 48 chemicals columns, distillation 33 databases 74–75 Compendium of Organic Synthetic accessed by SciFinder Scholar 88 Methods 105 spectroscopic data collections composition, elemental 64, 65, 67 108–110 Comprehensive Organic Chemistry see also CrossFire Beilstein; 106 Crossfi re Gmelin; SciFinder Comprehensive Organic Functional Scholar; Web of Science Group Transformations 106 decalin 172 Comprehensive Organic Synthesis deuterated compounds 142 106 deuterium 142 Comprehensive Organic diastereoisomers 20, 23, 138 Transformations 105 diborane 134 Comprehensive Organometallic 1,2-dichloroethane 172 Chemistry 106 dichloromethane 59, 172 concentration limits 13–14 diethyl carbonate 173 condensers 33 diethyl ether 173 continuous solvent extraction 59 diethylaluminium cyanide 130 cooling methods 137 diethylene glycol dimethyl ether 173 coupling constants 64, 70 diisobutylaluminium hydride 134 CRC Handbook of Chemistry and diisopropyl ether 175–176 Physics 108 1,2-dimethoxyethane 174 CrossFire Beilstein 75–76 dimethyl sulfate 12 search by graphical input 77–83 N,N-dimethylformamide 174–175 search by name 83–84 dimethylsulphoxide 175 INDEX 195

1,4-dioxan 175 ethyl formate 177–179 disposal and destruction 147–150 ethylene chloride 172 deactivating unknown chemicals ethylene glycol 177 155–156 ethylene glycol dimethyl ether 174 destroying known chemicals ethylene glycol monoethyl ether 177 (alphabetical list) 149–155 ethylene glycol monomethyl ether 177 substances for treating dangerous exposure limits 13–14 material 149 extraction and isolation dissolution 21–22 apparatus 58–59 distillation 27 continuous 59 apparatus 30–34 fl ow diagrams for mixtures 58, 59, azeotropes 35 60 choice of pressure and temperature mixtures according to acidity 30 56–58 Clausius-Clapeyron relationship 28 Nernst partition equation 56–57 fractional 29–30 organic substance from aqueous Raoult’s Law 28–29 phase 58–59 record 34 purifi cation and identifi cation theoretical plates 30 summary 61 DMF 174–175 eye injuries 4 DMSO 175 double-bond equivalence 66 F Drierite 162 fi ltration 22, 24 drying agents 160–165 under inert gas 132–133 azeotropic removal of water 35 fi res and fl ames 2 dyglyme 173 fi rst aid 4–7 fl ash chromatography 49–51 E fl ask, distillation 33 elemental composition 64, 65, 67 formamide 178 eluents formdimethylamide 174–175 classifi ed 39, 44, 45 fractional crystallisation 23–24 column chromatography 42 empirical formula 65 G enatiomorphic purity, determination glass apparatus 3 of 139–140 glycerine 178 ethane-1,2-diol 177 ethanoic acid 166 H ethanoic acid anhydride 167 halogens, test for 156 ethanol 176 handbooks 107–108 ether 175–176 hazard symbols 17 ether extraction 57, 58–59 hazardous chemicals 2 2-ethoxyethanol 177 biological exposure limits 15–16 ethyl acetate 59, 176 carcinogens 14–16 ethyl alcohol 176 concentration limits 12–14, 15 ethyl cellosolve 177 disposal and destruction 147–148 196 INDEX

hazardous chemicals (continued) light petroleum 181 deactivating unknown chemicals liquid nitrogen 3 155–156 literature search 73–74 destroying known chemicals citation search 103–105 (alphabetical list) 149–155 databases 74–75 radioactive waste 157 CrossFire Beilstein 75–86 handling 4 CrossFire Gmelin 86–88 online information 16–17 SciFinder Scholar 88–102 poisons 10–13, 150 spectroscopic data collections R and S Phrases 11–12, 185–191 108–110 substances for treating dangerous Web of Science 102–105 material 149 monographs, reference works and health and safety see under hazardous handbooks 107–108 chemicals primary literature 74 heating baths 32–33 Registry Number 58 Heilbron’s Dictionary of Organic reviews 105–107 Compounds 108 secondary literature 74 hexamethylphosphortriamide 12–13, strategy 74 178 lithium alkyls 137 n-hexane 178 lithium aluminium deuteride 142 HMPA 178 lithium aluminium hydride 134 HPLC 51 drying agent 164 and class of substance 52 lithium borodeuteride 142 procedure 52–53 lithium sand 135 theoretical plates 53–54 low temperatures, working at 136 cryostatic slush baths 137–138 I recrystallisation 136 inert gas, operations under 129–132 temperature control and cooling 137 infrared spectroscopy 63–64, 66, 67, 69 M data collections 108 magnesium 162 isotopically labelled compounds, magnesium sulphate 162 synthesis of manometer 34 radioisotopes 143 mass spectrometry 64, 66, 67, 68–69 stable isotopes 140–142 data collections 108 MEDLINE 89 K melting point Karl Fischer titration 165 and crystallisation 19–20, 25 kieselgel 38–39, 44 mixed 25–26 drying agent 164 Merk Index 108 methanol 179 L 2-methoxyethanol 177 laboratory notebooks 111–115 methyl acetate 180 laboratory safety see safety methyl alcohol 179

LD50 values 10–11 methyl benzene 183 INDEX 197 methyl cellosolve 177 chromatography 37–39 methyl ethyl ketone 169–170 crystallisation 20, 24–25 methyl iodide 13 Nernst partition equation 56–57 methyl iso-butyl ketone 180 phenols 56 methylene chloride 172–173 phenyl methyl ether 168 4-methylpentan-2-one 180 phosphorus pentoxide 166 2-methylpropan-1-ol 169 poisons 2-methylpropan-2-ol 169 classifi cation 10–11 mixed melting point 25–26 defi ned 10 molecular formula 68–69 EU regulations 11–13 molecular ion 64, 65, 68, 70 fi rst aid 7 molecular sieves 162 LD50 values 10–11 molecular weight 65 R Phrases 11–12, 185–187 monoglyme 176 S Phrases 12, 189–191 monographs 107–108 see also hazardous chemicals mother liquor 24 polarimetry 139 potassium 135 N potassium carbonate 164 Nernst partition equation 56–57 potassium hydride 134 neutron diffraction 26 potassium hydroxide 164 nitrobenzene 180 preparative TLC 41–42 nitrogen 133 pressure liquid 3 and boiling point 28 NMR spectroscopy 64, 66, 68, 69–70 choice for distillation 30 data collections 108–110 propan-1-ol 181 and enantiomorphic purity 139 propan-2-ol 181 notebooks 111–115, 129 propane-1,2,3-triol 178 nuclear magnetic resonance see NMR n-propyl alcohol 181 spectroscopy iso-propyl alcohol 181 nucleation 23 pumps 34 O purifi cation 128 and identifi cation summary 61 occupational exposure standard 13–14 solvents (alphabetical list) 167–185 and carcinogens 15 see also chromatography; optical activity 139 crystallisation; distillation; Organic Reactions 105 extraction Organic Syntheses 106 purity organic synthesis see synthesis oxidation test 156 enantiomorphic 139 and melting point 20, 25–26 P pyridine 181–183 n-pentane 180–182 peroxides, removal of 161 R petroleum ether 181 Rf values 41 phases R Phrases 11–12, 185–187 198 INDEX

racemates 20, 23, 141–142 Sikkon 162 radioactive waste 157 silica gel 45, 46 radioisotopes 143 drying agent 164 Raoult’s Law 28 simple distillation see distillation reaction slush baths 137–138 optimising conditions 128 smoking 3 parameters 126 sodium 164 Reagents for Organic Synthesis 106 sodium borodeuteride 142 receiver adaptor 33–34 sodium fusion test 156 rectifi cation 29–30 sodium hydride 164 reference works 107–108 sodium sand 135 Registry Numbers 88 sodium sulfate 165 report writing solvent extraction see extraction and example report 119–123 isolation required features 115–117 solvents see also notebooks crystallisation 21–22 reviews 105–107 degassing 130 disposal and recovery 127 S drying agents 164 S Phrases 12, 189–191 eluents 39, 44 safety, laboratory 1–2 properties and purifi cation equipment and procedures 2–3 (alphabetical list) 166–183 fi rst aid 4–7 Soxhlet apparatus 59 handling chemicals 4 Specialist Periodical Reports of the online information 8 Royal Society of Chemistry see also hazardous chemicals 107 ‘sandwich technique’ 145 spectroscopic methods see structure Science Citation Index 102–103 determination Science of Synthesis, Houben–Weyl spectroscopy data collections Methods of Molecular 108–110 Transformations 106 structure determination 63 SciFinder Scholar elemental composition 64, 65, databases accessed 88 67 formulating effective search input example procedure 65–70 98–99 fl ow diagram of procedure 65 linked concepts 99–100 infrared spectroscopy 63 literature references by author mass spectrometry 64, 66, 67, 101–102 68–69 search for a reaction 96–97 NMR spectroscopy 64, 66, 68, search for a theme 96–98 69–70 substructure search for papers 90–96 ultraviolet spectroscopy 64–65, 66, technical features 89–90 67, 69 searching literature see literature visible spectroscopy 64–65 search sublimation 20 INDEX 199 sulfur dioxide 182 V sulpholane 182 vacuum work 3 supersaturated solutions 23 vapour pressure 28–29 synthesis of organic compounds visible spectroscopy 64–65, 66 124–125 data collections 108 air-sensitive substances, handling 129–135 W chiral compounds 138–140 waste material 148 choosing and planning synthetic disposal 127–128 route 124–128 water bath 32 fl ow charts 127 water- and air-sensitive substances isotopically labelled compounds 129 140–142 choice of inert gas 129 optimising conditions 128 crystallisation 133–134 purifi cation and characterisation degassing solvents 131 128 diborane 134 water-sensitive substances, handling diethylaluminium cyanide 134 129–135 diisobutylaluminium hydride 134 Synthetic Methods for Organic fi ltration 133–134 Synthesis 105–106 lithium alkyls 134 lithium aluminium hydride 134 T lithium sand 135 Techniques of Chemistry 107 potassium 135 temperature control 137 potassium hydride 134 tetrahydrofuran 182 reaction vessel preparation 130–131 tetrahydronaphthalene 182–183 sodium sand 135 tetralin 182–183 storage of chemicals 134 theoretical plates transfer of liquids 131 distillation 30 transfer of solids 132 HPLC 53–54 Web of Science 75, 102 THF 182 example citation search 103–105 thick-layer chromatography 41–42 Science Citation Index 102–103 thin-layer chromatography 40–41 work-up and isolation 126 toluene 183 writing a report 1,2,3-trihydroxypropane 178 example report 122–124 tritium compounds 142–143 required features 115–117 see also notebooks U ultraviolet spectroscopy 64–65, 66, X 67, 69 X-ray diffraction 26 data collections 108 xylene 183

With kind thanks to W. F. Farrington for creation of this index.