Tables of Unknowns and Derivatives

[Pages:10]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 1?7. 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 40?C. 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 2??3?C 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 derivative's 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

Part 4 ? Organic Qualitative Analysis

T A B L E 1 Alcohols

Compound

bp, ?C

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-methyl-

2-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

mp, ?C

25

19 25

20 33 24 24 43

3,5-Dinitrobenzoate

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

1-Naphthylurethane

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

Phenylurethane

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

Appendix ? Tables of Unknowns and Derivatives

359

T A B L E 1 Alcohols (continued)

Compound

bp, ?C

mp, ?C

2,2-Dimethyl-1-

propanol

113

53

Diphenylmethanol

(benzhydrol)

288

69

Benzoin

133 (137)

()-Cholesterol

148

()-Borneol

208

3,5-Dinitrobenzoate

----

141 ---- ---- 154

1-Naphthylurethane

100

135 140 176 132

Phenylurethane

144

139 165 168 138

T A B L E 2 Aldehydes

Compound

Propanal 2-Butenal (trans) Hexanal Heptanal 2-Furancarboxaldehyde Cyclohexane-

carboxaldehyde Octanal Benzaldehyde Phenylethanal 2-Hydroxy-

benzaldehyde 4-Methylbenzaldehyde 2-Chlorobenzaldehyde 3-Phenylpropanal 3-Bromobenzaldehyde 2-Methoxybenzaldehyde 4-Methoxybenzaldehyde Cinnamaldehyde (trans) 3,4-Methylenedioxy-

benzaldehyde 3,4-Dimethoxy-

benzaldehyde 4-Chlorobenzaldehyde 4-Bromobenzaldehyde 3-Nitrobenzaldehyde 4-Hydroxy-3-methoxy-

benzaldehyde (Vanillin) 3-Hydroxybenzaldehyde 4-Hydroxybenzaldehyde

bp, ?C

49 103 128 155 161

161 171 179 194

196 204 213 224 235 245 247 252

263

214

mp, ?C

34

38

37 44 47 56 58 80 104 115

2,4-Dinitrophenylhydrazone

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

Semicarbazone

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

360

Part 4 ? Organic Qualitative Analysis

T A B L E 3 Amines

Compound

Classa bp, ?C mp, ?C Benzamideb Benzenesulfonamideb

Picrateb

tert-Butylamine

1?

46

Propylamine

1?

49

Diethylamine

2?

55

Allylamine

1?

58

sec-Butylamine

1?

63

2-Amino-2-methylbutane 1?

77

Butylamine

1?

77

Diisopropylamine

2?

83

Pyrrolidine

2?

89

Triethylamine

3?

89

1-Aminopentane

1?

104

Piperidine

2?

105

Dipropylamine

2?

110

Ethylenediamine

1?

116

1-Aminohexane

1?

129

Morpholine

2?

130

Diisobutylamine

2?

138

2-Aminoheptane

1?

143

1-Aminoheptane

1?

155

Tripropylamine

3?

156

Dibutylamine

2?

160

1-Amino-2-propanol

1?

163

Indole-3-acetic acid

2?

168

2-Fluoroaniline

1?

176

N,N-Dimethylbenzylamine 3?

182

N-Methylbenzylamine

2?

182

Benzylamine

1?

184

4-Fluoroaniline

1?

186

1-Phenylethylamine

1?

187

2-Phenylethylamine

1?

198

Tributylamine

3?

216

4-Aminomethylpyridine

1? (3?) 230

Aminodiphenylmethane 1?

295

2-Amino-6-methylpyridine 1? (3?) 208

41

2-Benzoylpyridine

3?

42

4-Methylaniline

1?

200

45

2-Aminobiphenyl

1?

49

6-Amino-1-hexanol

1?

57

Methoxyaniline

1?

58

4-Bromoaniline

1?

245d 66

4-Iodoaniline

1?

67

2-Nitroaniline

1?

71

4-Chloroaniline

1?

72

Tribenzylamine

3?

91

3-Nitroaniline

1?

113

2,4,6-Tribromoaniline

1?

119

3-Aminophenol

1?

122

3-(Dimethylaminomethyl)-

indole

3?

133

2-Aminobenzoic acid

1?

146

4-Nitroaniline

1?

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

TABLE 3 Compound

Amines (continued)

Classa

bp, ?C mp, ?C Benzamideb Benzenesulfonamideb

Picrateb

3-Aminobenzoic acid

1?

2-Aminophenol

1?

4-Aminophenol

1?

4-Aminobenzoic acid

1?

-Alanine

1?

Glycine

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 4 Carboxylic acids

Compound

bp, ?C

mp, ?C

MW

Amide

Anilide

Formic acid

100

46 ----

50

Acetic acid

118

60 82

114

Propanoic acid

140

74 81

105

Chloroacetic acid

185

61

94 121

135

2-Chloropropanoic acid

186

108 80

92

Dichloroacetic acid

194

128 98

118

2-Bromopropanoic acid

204

24

153 123

99

Bromoacetic acid

208

50

139 91

131

Octanoic acid

236

144 110

57

Decanoic acid

270

30

172 108 (100)

70

3-Chloropropanoic acid

41

107 101

----

Dodecanoic acid (lauric acid)

43

200 99

78

3-Phenylpropanoic acid

280

48 (40) 110 82 (105)

96

Trichloroacetic acid

57

163 141

97

2-Butenoic acid (trans)

72

86 160

118

Phenylacetic acid

76

136 156

117

2-Benzoylbenzoic acid (monohydrate)

90

208 165

195

(anhydrous, 128) 226

Pentanedioic acid (glutaric acid)

97

132 175 (di)

224 (di)

Phenoxyacetic acid

99

152 101

99

2-Methoxybenzoic acid

100

152 129

----

Citric acid (monohydrate)

100

210 210 (tri)

192 (tri)

(anhydrous, 153) 192

Oxalic acid (dihydrate)

104

126 419d (di)

254 (di)

4-Chlorophenylacetic acid

105

170 175

164

2-Methylbenzoic acid

105

136 142

125

3-Methylbenzoic acid

111

136 94

126

(1)- or (2)-Mandelic acid

118

152 133

151

3-Furancarboxylic acid

121

112 169

----

Benzoic acid

122

122 130

160

Maleic acid

130

116 260 (181) (di) 187 (di)

Cinnamic acid (trans)

133

148 147

153 (109)

2-Furancarboxylic acid

134

112 143

123

Decanedioic acid (sebacic acid)

134

202 210 (di)

202 (di)

362

Part 4 ? Organic Qualitative Analysis

T A B L E 4 Carboxylic acids (continued)

Compound

bp, ?C

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

mp, ?C

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

MW

Amide

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)

Anilide

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 5 Esters

Compound

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

bp, ?C

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

mp, ?C

Appendix ? Tables of Unknowns and Derivatives

T A B L E 5 Esters (continued)

Compound

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)

bp, ?C

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

mp, ?C

29

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

363

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Part 4 ? Organic Qualitative Analysis

T A B L E 6 Ketones

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

bp, ?C

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

mp, ?C

27 20 27 20 28 37 33 42 48

2,4-Dinitrophenyl hydrazone

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 ----

Semicarbazone

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) ---- ----

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