APPENDIX

Tables of Unknowns and Derivatives

The following tables list several hundred organic compounds and provide representative examples of the six functional-group classes that are treated in Part 4, Organic Qualitative Analysis. The functional groups appear in alphabetical order in Tables 17. In each table, compounds are listed in order of increasing boiling points; solids appear last in each table in order of increasing melting points. Compounds are arbitrarily listed by increasing boiling points unless their melting points are above 40C. Many pure compounds that melt just above room temperature may be in the liquid state when you encounter them due to depression of their melting points by impurities. Remember also that the melting points we list may be 23C higher or even more than the values you measure, because the listed melting points are those of the purified compounds. When a derivative has been reported to decompose on melting, a "d" marks the melting point. When no solid derivative is listed in standard reference tables for an alcohol, aldehyde, ketone, amine, carboxylic acid, or phenol, a dash appears in the table in place of the derivatives melting point. In a few cases, two widely different melting points for a compound are listed in the literature; we include both, the second one in parentheses. The derivatives of multifunctional compounds that can form through derivatization at more than one site are shown by the notation "(mono)," "(di)," or "(tri)" after the melting point.

357

358
T A B L E Compound 1

Part 4 Organic Qualitative Analysis

Alcohols
bp, C mp, C 3,5-Dinitrobenzoate 1-Naphthylurethane Phenylurethane

Methanol Ethanol 2-Propanol 2-Methyl-2-propanol 2-Propen-1-ol 1-Propanol 2-Butanol 2-Methyl-2-butanol 2-Methyl-1-propanol 1-Butanol 3-Pentanol 2-Pentanol 3-Methyl-3-pentanol 2-Methoxyethanol 1-Chloro-2-propanol 2-Methyl-1-butanol 3-Methyl-1-butanol 2-Chloroethanol 4-Methyl-2-pentanol 2-Ethoxyethanol 3-Hexanol 1-Pentanol 2-Hexanol Cyclopentanol 3-Hydroxy-2-butanone 2,2,2-Trichloroethanol 1-Hexanol 2-Heptanol Cyclohexanol 1-Amino-2-propanol 4-Hydroxy-4-methyl2-pentanone 2-Furylmethanol 1-Heptanol 2-Octanol 1,2-Propanediol 1-Octanol 1,2-Ethanediol 1-Phenylethanol Benzyl alcohol 1,3-Propanediol 2-Phenylethanol 1-Decanol 3-Phenyl-1-propanol Cinnamyl alcohol 1-Dodecanol (lauryl alcohol) 4-Methoxybenzyl alcohol Glycerol ()-Menthol

65 78 83 83 97 97 99 102 108 116 116 119 123 124 127 129 131 131 132 135 135 138 139 140 145 151 157 159 161 163 166 171 176 179 187 194 197 202 205 214 219 231 236 257 259 259 290d

25

19

25

107 93 122 142 49 74 75 116 86 64 99 61 96 (62) 77 70 61 95 65 75 97 (77) 46 38 115 142 58 49 112 55 80 47 32 61 169 (di) 93 112 178 (di) 108 57 92 121 60 153

124 79 106 101 108 80 97 72 104 71 95 74 83 112 82 68 101 88 67 68 60 118 120 60 54 129 130 62 63 153 (di) 67 176 (di) 106 134 164 (di) 119 73 114 80 191 (tri) 119

47 52 76 136 70 57 65 42 86 61 48 43 31 55 51 143 46 132 87 42 82 45 60 114 74 157 (di) 92 77 137 (di) 78 59 45 90 74 92 180 (tri) 111

20

33 24 24 43

Appendix Tables of Unknowns and Derivatives

359

T A B L E Compound

Alcohols (continued)
bp, C mp, C 3,5-Dinitrobenzoate 1-Naphthylurethane Phenylurethane

2,2-Dimethyl-1propanol Diphenylmethanol (benzhydrol) Benzoin ()-Cholesterol ()-Borneol

113 288

53 69 133 (137) 148 208

141 154

100 135 140 176 132

144 139 165 168 138

T A B L E Compound

Aldehydes
bp, C mp, C 2,4-Dinitrophenylhydrazone Semicarbazone

Propanal 2-Butenal (trans) Hexanal Heptanal 2-Furancarboxaldehyde Cyclohexanecarboxaldehyde Octanal Benzaldehyde Phenylethanal 2-Hydroxybenzaldehyde 4-Methylbenzaldehyde 2-Chlorobenzaldehyde 3-Phenylpropanal 3-Bromobenzaldehyde 2-Methoxybenzaldehyde 4-Methoxybenzaldehyde Cinnamaldehyde (trans) 3,4-Methylenedioxybenzaldehyde 3,4-Dimethoxybenzaldehyde 4-Chlorobenzaldehyde 4-Bromobenzaldehyde 3-Nitrobenzaldehyde 4-Hydroxy-3-methoxybenzaldehyde (Vanillin) 3-Hydroxybenzaldehyde 4-Hydroxybenzaldehyde

49 103 128 155 161 161 171 179 194 196 204 213 224 235 245 247 252 263

150 190 104 108 229 (212) 172 106 237 121 248 232 212 149 253 254 255d 266d 262 254 257 293d 271d 257d 280d

89 (154) 199 106 109 202 173 98 222 153 231 234 (215) 225 (146) 127 205 215d 210 215 230 177 230 228 246 229 198 224

34

38

37 44 47 56 58 80 104 115

214

360
T A B L E Compound 3

Part 4 Organic Qualitative Analysis

Amines
Classa bp, C mp, C Benzamideb Benzenesulfonamideb Picrateb

tert-Butylamine Propylamine Diethylamine Allylamine sec-Butylamine 2-Amino-2-methylbutane Butylamine Diisopropylamine Pyrrolidine Triethylamine 1-Aminopentane Piperidine Dipropylamine Ethylenediamine 1-Aminohexane Morpholine Diisobutylamine 2-Aminoheptane 1-Aminoheptane Tripropylamine Dibutylamine 1-Amino-2-propanol Indole-3-acetic acid 2-Fluoroaniline N,N-Dimethylbenzylamine N-Methylbenzylamine Benzylamine 4-Fluoroaniline 1-Phenylethylamine 2-Phenylethylamine Tributylamine 4-Aminomethylpyridine Aminodiphenylmethane 2-Amino-6-methylpyridine 2-Benzoylpyridine 4-Methylaniline 2-Aminobiphenyl 6-Amino-1-hexanol Methoxyaniline 4-Bromoaniline 4-Iodoaniline 2-Nitroaniline 4-Chloroaniline Tribenzylamine 3-Nitroaniline 2,4,6-Tribromoaniline 3-Aminophenol 3-(Dimethylaminomethyl)indole 2-Aminobenzoic acid 4-Nitroaniline

1 1 2 1 1 1 1 2 2 3 1 2 2 1 1 2 2 1 1 3 2 1 2 1 3 2 1 1 1 1 3 1 (3) 1 1 (3) 3 1 1 1 1 1 1 1 1 3 1 1 1 3 1 1

46 49 55 58 63 77 77 83 89 89 104 105 110 116 129 130 138 143 155 156 160 163 168 176 182 182 184 186 187 198 216 230 295 208 200

245d

41 42 45 49 57 58 66 67 71 72 91 113 119 122 133 146 147

134 84 42 76 42 48 244 (di) 40 75 113 105 185 120 116 90 158 102 154 204 222 110 192 155 198 174 (198) 182 199

36 42 39 70 93 51 168 (di) 96 118 55 88 69 120 95 134 104 122 136 139

198 135 155 140 139 183 151 140 112 (163) 173 139 152 75 233 (di) 126 146 121 121 116 59 142 93 117 194 174 106 202 130 182 180 73 190 143 104 100

Appendix Tables of Unknowns and Derivatives

361

T A B L E Compound

Amines (continued)
Classa bp, C mp, C Benzamideb Benzenesulfonamideb Picrateb

3-Aminobenzoic acid 2-Aminophenol 4-Aminophenol 4-Aminobenzoic acid -Alanine Glycine

1 1 1 1 1 1

173 174 184 189 200d 230d

248 234 (di) 278 120 188

141 125

202

a. 1, primary; 2, secondary; 3, tertiary. b. Procedures for preparation of derivatives can be found in Ref. 1.

T A B L E Compound

Carboxylic acids
bp, C mp, C MW Amide Anilide

Formic acid Acetic acid Propanoic acid Chloroacetic acid 2-Chloropropanoic acid Dichloroacetic acid 2-Bromopropanoic acid Bromoacetic acid Octanoic acid Decanoic acid 3-Chloropropanoic acid Dodecanoic acid (lauric acid) 3-Phenylpropanoic acid Trichloroacetic acid 2-Butenoic acid (trans) Phenylacetic acid 2-Benzoylbenzoic acid (monohydrate) Pentanedioic acid (glutaric acid) Phenoxyacetic acid 2-Methoxybenzoic acid Citric acid (monohydrate) Oxalic acid (dihydrate) 4-Chlorophenylacetic acid 2-Methylbenzoic acid 3-Methylbenzoic acid (1)- or (2)-Mandelic acid 3-Furancarboxylic acid Benzoic acid Maleic acid Cinnamic acid (trans) 2-Furancarboxylic acid Decanedioic acid (sebacic acid)

100 118 140 185 186 194 204 208 236 270

280

46 50 60 82 114 74 81 105 61 94 121 135 108 80 92 128 98 118 24 153 123 99 50 139 91 131 144 110 57 30 172 108 (100) 70 41 107 101 43 200 99 78 48 (40) 110 82 (105) 96 57 163 141 97 72 86 160 118 76 136 156 117 90 208 165 195 (anhydrous, 128) 226 97 132 175 (di) 224 (di) 99 152 101 99 100 152 129 100 210 210 (tri) 192 (tri) (anhydrous, 153) 192 104 126 419d (di) 254 (di) 105 170 175 164 105 136 142 125 111 136 94 126 118 152 133 151 121 112 169 122 122 130 160 130 116 260 (181) (di) 187 (di) 133 148 147 153 (109) 134 112 143 123 134 202 210 (di) 202 (di)

362
T A B L E Compound 4

Part 4 Organic Qualitative Analysis

Carboxylic acids

(continued)
bp, C mp, C MW Amide Anilide

Acetylsalicylic acid 2-Chlorobenzoic acid 3-Nitrobenzoic acid 2-Nitrobenzoic acid 2-Aminobenzoic acid Diphenylacetic acid Benzilic acid 2-Bromobenzoic acid Hexanedioic acid (adipic acid) 3-Chlorobenzoic acid 2-Hydroxybenzoic acid (salicylic acid) 1-Naphthoic acid 2-Iodobenzoic acid 2,4-Dichlorobenzoic acid (1)-Tartaric acid 4-Methylbenzoic acid 3,4-Dimethoxybenzoic acid 4-Methoxybenzoic acid Butandioic acid (succinic acid) 4-Aminobenzoic acid Hippuric acid (N-benzoylglycine) -Alanine Phthalic acid 4-Hydroxybenzoic acid Glycine 4-Nitrobenzoic acid 4-Chlorobenzoic acid Fumaric acid

136 140 140 146 146 148 150 150 153 158 159 160 162 162 169 180 182 184 185 189 190 200d 206d 215 230d 241 242 286

180 138 156 142 (202) 167 142 167 174 136 109 212 168 228 153 201 155 146 220 (di) 156 134 138 139 172 203 248 110 191 194 150 195 (di) 136 160 182 164 152 167 118 260 (di) 136 179 183 89 166 220 (di) 138 162 75 167 201 156 179 116 266 (di)

136 114 153 155 131 180 174 141 240 (di) 122 136 163 141 263 (di) 145 154 169 230 (di) 208 253 (di) 196 211 194 313 (di)

T A B L E Compound

Esters
bp, C mp, C

Ethyl formate Methyl acetate Ethyl trifluoroacetate Ethyl acetate tert-Butyl acetate Propyl acetate Allyl acetate 1-Methylpropyl acetate 2-Methyl-1-propyl acetate Methyl 2-butenoate (trans) 1-Butyl acetate 3-Methyl-1-butyl acetate 1-Butyl propanoate 1-Pentyl acetate Ethyl 2-oxopropanoate

54 57 61 77 98 101 103 112 117 119 126 142 146 149 155

Appendix Tables of Unknowns and Derivatives

363

T A B L E Compound

Esters

(continued)
bp, C mp, C

Ethyl hexanoate Ethyl trichloroacetate Methyl acetoacetate 2-Furylmethyl acetate Ethyl acetoacetate Methyl 2-furoate Dimethyl butanedioate Phenyl acetate Methyl benzoate 4-Hydroxybutanoic acid lactone Ethyl 4-oxopentanoate 4-Hydroxypentanoic acid lactone Ethyl benzoate Benzyl acetate Diethyl butanedioate Diethyl (E)-2-butenedioate Diethyl (Z)-2-butenedioate Methyl 2-hydroxybenzoate ()-Bornyl acetate Ethyl 2-hydroxybenzoate 1-Butyl 4-oxopentanoate Ethyl decanoate 1-Butyl benzoate Glyceryl triacetate Ethyl benzoylacetate Ethyl dodecanoate Ethyl cinnamate (trans) Dimethyl phthalate Dibutyl phthalate Benzyl benzoate Methyl 3-pyridinecarboxylate Phenyl 2-hydroxybenzoate 1-Naphthyl acetate Methyl 2-hydroxy-2-phenylacetate Phenyl benzoate Diphenyl phthalate Cholesteryl acetate Ethyl 4-hydroxybenzoate Acetylsalicylic acid (Aspirin)

168 168 170 176 181 181 196 197 199 204 206 207 213 216 217 218 222 223 223 234 237 244 250 258 265 269 271 284 340 323 209

29

21 42 42 48 52 70 75 116 (94) 116 136

364
T A B L E 6

Part 4 Organic Qualitative Analysis

Ketones
bp, C mp, C 2,4-Dinitrophenyl hydrazone Semicarbazone

Compound

Acetone 2-Butanone 2,3-Butanedione 3-Methyl-2-butanone 2-Pentanone 3-Pentanone 3,3-Dimethyl-2-butanone (pinacolone) 4-Methyl-2-pentanone 2,4-Dimethyl-3-pentanone 3-Hexanone 2-Hexanone Cyclopentanone 2,4-Pentanedione 4-Heptanone 3-Hydroxy-2-butanone (acetoin) 3-Heptanone 2-Heptanone Ethyl 2-oxopropanoate Cyclohexanone 4-Hydroxy-4-methyl-2-pentanone 3-Octanone 2,6-Dimethyl-4-heptanone 3-Methylcyclohexanone Methyl acetoacetate 4-Methylcyclohexanone 2-Octanone Ethyl acetoacetate Cycloheptanone 5-Nonanone 2,5-Hexanedione 2,6-Dimethyl-2,5-heptadien-4-one (phorone) Acetophenone Ethyl 4-oxopentanoate 1-Phenyl-2-propanone Propiophenone 2-Methyl-1-phenyl-1-propanone 1-Phenyl-2-butanone 4-Methylacetophenone ()-Carvone 4-Chloroacetophenone Butyl 4-oxopentanoate 4-Methoxyacetophenone Ethyl benzoylacetate 1-Acetylnaphthalene 1,3-Diphenylacetone 2-Benzoylpyridine Benzoin methyl ether

56 80 88 94 102 102 106 116 125 125 129 131 139 144 145 148 151 155 156 166 167 168 169 170 171 172 181 181 187 194 198 204 206 216 218 222 226 226 230 232 237 258 265 302 330 27 20 27 20

126 117 314 (di) 120 144 156 125 95 95 130 106 (110) 146 209 (di) 75 318 89 162 203 66 (92) 155 134 58 93 148 257 (di) 118 240 (250) 102 156 191 163 260 191 231 220 (231) 100 199

28

37

33 42 48

190 136 278 (di) 235 (mono) 113 110 139 157 133 160 113 12 210 209 (di) 122 (mono) 133 185 (202) 103 (152) 127 166 126 179 (191) 152 199 122 133 163 90 224 (di) 185 (mono) 221 (186) 198 148 199 174 181 135 (146) 205 162 204 (160) 197 125 289 (233) 146 (126)

Appendix Tables of Unknowns and Derivatives

365

T A B L E

Ketones

(continued)
2,4-Dinitrophenyl hydrazone

Compound

bp, C

mp, C

Semicarbazone

Benzophenone 4-Bromoacetophenone 2-Acetylnaphthalene 1,3-Diphenyl-2-propen-1-one (benzalacetophenone) Benzoin ethyl ether 4-Methoxybenzophenone 4-Nitroacetophenone 3-Nitroacetophenone Fluorenone Benzil 2-Benzoylbenzoic acid Benzoin 4-Hydroxybenzophenone ()-Camphor ()-Camphor Ninhydrin

48 51 53 58 60 62 80 81 83 95 128 133 (137) 134 174 180 243

239 (229) 230 (237) 262 244 180 228 283 189 (di) 245 242 164 177

164 208 235 170 (179) 257 234 244 (di) 174 (mono) 206 194 247 (237)

T A B L E

Phenols
bp, C mp, C Bromo derivative 1-Naphthylurethane 3,5-Dinitrobenzoate

Compound

2-Hydroxybenzaldehyde 2-Methoxyphenol (guaiacol) 4-Chlorophenol Methyl 2-hydroxybenzoate 2-tert-Butylphenol Ethyl 2-hydroxybenzoate Phenyl 2-hydroxybenzoate 2-Nitrophenol 5-Methyl-2-isopropylphenol (thymol) 4-Hydroxy-3-methoxybenzaldehyde (vanillin) 1-Naphthol 4-tert-Butylphenol 3-Hydroxybenzaldehyde 1,2-Dihydroxybenzene (catechol) 1,3-Dihydroxybenzene (resorcinol) 2-Chloro-4-nitrophenol 4-Nitrophenol 4-Hydroxybenzaldehyde Ethyl 4-hydroxybenzoate

196 205 217 223 224 234

32 37 (43)

42 45 50 80 94 100 104 106 110 111 114 116 116

116 (tri) 90 (di) 117 (di) 55 (mono) 160 105 (di) 65 (di) 192 (tetra) 112 (di) 142 (di) 181 (di)

118 166 113 160 152 110 175 206 151

141 186 155 103 217 152 (di) 201 (di) 186

366
T A B L E 7

Part 4 Organic Qualitative Analysis

Phenols

(continued)
Bromo derivative 1-Naphthylurethane 3,5-Dinitrobenzoate

Compound

bp, C

mp, C

1,3,5-Trihydroxybenzene (phloroglucinol) 3-Aminophenol 2-Naphthol 1,2,3-Trihydroxybenzene (pyrogallol) 4-Hydroxybenzophenone 2-Hydroxybenzanilide 2-Hydroxybenzamide 2-Hydroxybenzoic acid (salicylic acid) 4-Acetamidophenol 1,4-Dihydroxybenzene (hydroquinone) 2-Aminophenol 4-Aminophenol 4-Hydroxybenzoic acid Phenolphthalein

117 (dihyd) 151 (tri) 219 (anhy) 122 123 84 133 134 136 141 159 169 171 174 184 215 265 158 (di) 186 (di)

156

179 210 205 (tri) 317 (di) 178