practical organic chemistry 5ed - vogel

10 PHYSICAL CONSTANTS OF ORGANIC COMPOUNDS

Table 10.11 Aromatic halogen compounds

CompoundQC

B.P.QC

M.P.QC

d'fl' nil'"

m-Difluorobenzene 83 1.153 1.439FIuorobenzene 85 1.024 1.466p-Difluorobenzene 89 1.166 1.441o-Difluorobenzene 93 1.157 1.443o-FIuorotol uene 114 0.998 1.470m-Fluorotoluene 116 0.990p-Fluorotoluene 116 0.998 1.469Chlorobenzene 132 1.107 1.525Bromobenzene 156 1.494 1.560o-Chlorotoluene 159 1.082 1.527m-Chlorotoluene 162 1.072 1.522p-Chlorotoluene 162 7 1.070 1.521m-Dichlorobenzene 173 1.288 1.546Benzyl chloride 179 1.100 1.5390-Dichlorobenzene 180 1.305 1.5510-Bromotoluene 181 1.425m-Bromotoluene 183 1.410p-Bromotoluene 185 26 1.390Iodobenzene 188 1.831 1.620o-Bromochlorobenzene 195 1.646 1.580Benzyl bromide 198 1.4382,4-Dichlorotoluene 199 1.249 1.5492,6-Dichlorotoluene 199 1.269 1.551m-Iodotoluene 204 1.698Benzyl iodide 93/10 24Benzylidene chloride 205 1.250 1.550o-Iodotoluene 207 1.6983,4-Dichlorotoluene 207 1.251 1.549Benzylidene bromide 156/23 1.460 1.5411,2,4-Trichlorobenzene 213 17 1.468 1.5542-Fluoronaphthalene 212 61l-Fluoronaphthalene 214 1.134 1.594m-Dibromobenzene 219 1.952 1.606Benzotrichloride 220 1.173o-Dibromobenzene 224 7 1.956 1.609Bromomesitylene 225 -12-Bromocymene 234 1.2672,5-Dibromotoluene 236 1.8113,4-Dibromotoluene 240 1.811 1.600r-Bromoiodobenzene 252Chloronaphthalene 256 61o-Bromoiodobenzene 257 2.262 1.665l-Chloronaphthalene 259 1.192 1.633l-Bromonaphthalene 281 1.484 1.658m-Di-iodobenzene 285 40o-Di-iodobenzene 287 272-Bromobiphenyl 297 1.2333-Bromobiphenyl 300 1.641l-Iodonaphthalene 302 1.7292-Iodobiphenyl 158/6 1.609 1.6622-Chlorobiphenyl 273 32

1322

TABLES OF DERIVATIVES 10

1323


Table 10.11 Aromatic halogen compounds (continued)

Compound B.P.C

M.P.c

1324

p-Iodotoluene 211 351,2-Dichloronaphthalene 296 35m-Di-iodobenzene 285 401,2,4-Tribromobenzene 275 44p-Dichlorobenzene 174 531,2,3-T richlorobenzene 218 532-Iodonaphthalene 309 542-Bromonaphthalene 282 592-Fluoronaphthalene 602,2'-Dichlorobiphenyl 602-Chloronaphthalene 256 611,3,5-Trichlorobenzene 208 63p-Bromochlorobenzene 195 671,2-Dibromonaphthalene 684-Fluorobiphenyl 253 744-Chlorobiphenyl 291 772,2'-Dibromobiphenyl 811,2,3-Tribromobenzene 884-Bromobiphenyl 310 89p-Dibromobenzene 219 89p-Bromoiodobenzene 251 924,4'-Difluorobiphenyl 255 954-Iodobiphenyl 1141,3,5-Tribromobenzene 271 120p-Di-iodobenzene 285 1291,2,4,5-Tetrachlorobenzene 240 1404,4'-Dichlorobiphenyl 1494,4'-Dibromobiphenyl 1641,2,4,5-Tetrabromobenzene 1811,2,3,4-Tetrachloronaphthalene 183Hexachlorobenzene 229


1325


Table 10.12 Aliphatic ethers

Ether B.P. QC tlfc. 20no

Diethyl 34 0.714 1.353Ethyl vinyl 36 0.759 1.377Allyl ethyl 67 0.765 1.388Di-isopropyl 68 0.726 1.368Butyl methyl 70 0.774 1.374Dipropyl 90 0.749 1.381Butyl ethyl 92 0.749 1.382Diallyl 94 0.803Pentyl methyl 99 0.761 1.387Cyclopentyl methyl 105 0.862 1.420Pentyl ethyl 118 0.762 1.393Di-s-butyl 121 0.764 1.396Cyclopentyl ethyl 122 0.853 1.423Di-isobutyl 123 0.756Hexyl methyl 126 0.772 1.397Cyclohexyl methyl 134 0.875 1.435Dibutyl 141 0.770 1.399Ethyl hexyl 142 0.772 1.401Cyclohexyl ethyl 149 0.864 1.435Di-isopentyl 171 0.778 1.409Cineole 176 0.923 1.458Dipentyl 188 0.785 1.412Dihexyl 229 0.793 1.420Diheptyl 259 0.801 1.427Dioctyl 288 0.806 1.433Didecyl 185/5mmHg 0.815 1.441

Chloromethyl methyl C 59 1.070 1.397l-Chloroethyl methyl 73 0.991 1.400Chloromethyl ethyl 83d 1.026 1.4042-Chloroethyl methyl 91 1.035 1.411sym-Dichlorodimethyl 105 1.310 1.4361,l'-Dichlorodiethyl 116 1.111 1.423Epichlorohydrin (I) C 117 1.181 1.4381,2-Dichlorodiethyl 140 1.177 1.4442,2'-Dichlorodiethyl 118 1.210 1.457Di-2-chloropropyl 188 1.109 1.447Di-J-chloropropyl 215 1.139 1.452

Ethyleneglycol dimethyl (2) 85 0.866 1.379Ethyleneglycol diethyl (2) 123 0.848Diethyleneglycol diethyl (2) 187 0.906 1.411Tetraethyleneglycol dimethyl (2) 266 1.009 1.432

Tetrahydrofuran 65 0.889 1.4072-Methyl tetrahydrofuran 79 0.855 1.407Dihydropyran 86 0.923 1.440Tetrahydropyran 88 0.881 1.421Dioxane 102 1.034 1.422

(1) 1-Chloro-2,3-epoxypropane.(2) For alternative names see Section 4.1.18, p. 406.

1327


Table 10.13 Aromatic ethers

Ether B.P. QC M.P. d'$'(JmmHg) QC

Furan 32 0.9372-Methylfuran 64 0.913Anisole 154 0.996Phenetole 170 0.965Benzyl methyl ether 171 0.965Methyl o-tolyl ether (1) 171 0.985Methyl p-tolyl ether 175 0.970Methyl m-tolyl ether 177 0.972Ethyl o-tolyl ether 184 0.953Benzyl ethyl ether 186 0.948Phenyl n-propyl ether 188 0.949Ethyl p-tolyl ether 190 0.949Ethyl m-tolyl ether 191 0.949Guaiacol (2) 205 28 1.129Veratrole (3) 206 22Butyl phenyl ether 208 0.934Thymol methyl ether 212Resorcinol dimethyl ether 217 1.050Safrole (4) 232 11 1.100Anethole (5) 235 22 0.989Resorcinol diethyl ether 235 12Eugenol methyl ether (6) 244 1.050Isosafrole (7) 248 7 1.122Diphenyl ether 259 28Isoeugenol methyl ether (8) 264 1.053Methyl I-naphthyl ether 271 1.092Ethyl l-naphthyl ether 280 5 1.060Dibenzyl ether 296 1.034

2-Methoxybiphenol 274 29Ethyl 2-naphthyl ether 282 37Pyrogallol triethyl ether 39Catechol diethyl ether 217 43Pyrogallol trimethyl ether 241 47Hydroquinone dimethyl ether 212 56Methyl 2-naphthyl ether 274 72Hydroquinone diethyl ether 72Benzyl l-naphthyl ether 774-Methoxybiphenyl 90Benzyl 2-naphthyl ether 99

Haloqeno-ethers

m-Chloroanisole 194o-Chloroanisole 195 1.191p-Chloroanisole 198m-Chlorophenetole 205 1.171o-Chlorophenetole 208 1.134o-Bromoanisole 210m-Bromoanisole 211p-Chlorophenet ole 212 21 1.121p-Bromoanisole 215 11o-Bromophenetole 218p-Bromophenetole 233 4o-lodoanisole 242

1328

1.545 131 Nitro,95151 Nitro,98

1.530 133 Nitro,82140 Nitro,l06

1.522 134 Nitro,61148 Nitro,88135 Nitro,98145 Nitro,47

TABLES OF DERIVATlVES 10

1329


Table 10.13 Aromatic ethers (continued)

Ether B.P. QC M.P.UmmHg) QC

Haloqeno-ethers (continued)

m-Iodoanisole 244o-Iodophenetole 246m-Iodophenetole 134/15p-Iodophenetole 252 29p-Bromodiphenyl ether 168/152,4,6-Trichlorophenetole 246 44p-Iodoanisole 240 522,4,6-Trichloroanisole 622,4,6-Tribromophenetole 732,4,6-Tribromoanisole 88

Nitro-ethers

o-Nitrophenetole 267o-Nitroanisole 272 10 1.254m-Nitrophenetole 284 34m-Nitroanisole 258 39p-Nitroanisole 259 54p- Nitrophenetole 283 602,4,6-Trinitroanisole 682,4,6-Trinitrophenetole 782,4-Dinitrophenetole 872,4-Dinitroanisole 94

(1) o-Methoxytoluene.(2) o-Methoxyphenol,(3) Catechol dimethyl ether.(4) l-Allyl-3,4-methylenedioxybenzene.

Table 10.14 Acetals

Name Formula B.P. QC tIl nil"4'

Methylal CHiOCH3h 43 0.859 1.353Dimethylacetal CH 3CH(OCH3h 64 0.852 1.366Ethylal CHiOC2Hsh 87 0.831 1.373Acetal CH 3CH(OC2H sh 103 0.826 1.381

1,3-Dioxane /0> 105 1.034 1.420H2C",-0 CH 2h

Isopropylal CHiOC3H 7ih 122 0.818 1.384

Ethylpropylal CH 3CH2CH(OC2Hsh 124 0.833 1.390Acrolein acetal CH 2=CHCH(OC2H sh 125 0.850Propylal CH 2(OC3H 7h 137 0.834 1.393

1330

Sulphonamide PicrateQC QC

131

1.562

(5) p-(l-propenyl)anisole.(6) l-Allyl-3,4-dimethoxybenzene.(7) 1,2-Methylenedioxy-4-(1-propenyl)benzene.(8) 3,4-Dimethoxy-l-(1-propenyl)benzene.

Other derivatives QC

NitrO,96

Nitro,96

Dinitro, 100

Dinitro,95Nitro,79

o-Phenetidine, 228o-Anisidine, 225m-Phenetidine, 248m-Anisidine, 251p-Anisidine, 246p-Phenetidine, 254


Name Formula RP. QC d'/l nlr'

Ethylbutylal CH3CH2CH2CH(OC2Hsh 143 0.921 1.402Propylacetal CH 3CH(OC3H7h 147 0.830 1.397Isobutylal CH 2(OC4H g'h 164 0.824 1.400Isobutylacetal CH 3CH(OC4Hg 'h 176 0.821 1.403Butylal CH 2(OC4Hgh 181 0.835 1.406Butylacetal CH3CH(OC4Hgh 187 0.833 1.409Pentylal CHiOCsH11h 219 0.838 1.416Pentylacetal CH3CH(OCsH Ilh 222 0.839 1.418Hexylal CHiOC6H I3h 255 0.841 1.423Benzaldehyde diethyl acetal C6H sCH(OC2Hsh 222 0.983 1.480

1331


Table 10.15 AIipha tic aldehydes

Aldehyde B.P. M.P. Alkylidene DimethoneQC QC dimethone anhydride

QC QC

Formaldehyde -21 189 171Acetaldehyde 20 141 174Propionaldehyde (propanal) 49 155 143Glyoxal 50 186 224Acrolein (propenal) 52 192 163Isobutyraldehyde (2-methy1propanal) 64 154 1442-Methylpropenal 73Butyraldehyde (butanal) 75 142 141Trimethylacetaldehyde 75Isovaleraldehyde (3-methylbutanal) 92 155 173Chloral (trichloroacetaldehyde) 98Crotonaldehyde (but-z-enal) 102 184 167Valeraldehyde (pentanal) 104 105 113Diethy1acetaldehyde 117 1024-Methylpentanal 121 133Paraldehyde 124Hexanal 131 109Tetrahydrofurfural 145Heptanal 155 103 112Furfural 161 162 164Hexahydrobenzaldehyde (I) 1622-Ethylhexanal 163Octanal 170 90 101Bromal (tribromoacetaldehyde) 174Nonanal 190 86(+ )-Citronellal 207 79 173Decanal 208 92Citral 229d{J-Hydroxybutyra1dehyde 83/20 147 126Chloral hydrate 53 56Lauraldehyde (2) 238 45Myristaldehyde (3) 155/10 23Palmitaldehyde (4) 201/29 34Stearaldehyde (5) 38( )-Glyceraldehyde 142

(1) Cyclohexanecarboxaldehyde.(2) Dodecanal.(3) Tetradecanal.(4) Hexadecanal.(5) Octadecanal.

1332


1333


Table 10.16 Aromatic aldehydes

Aldehyde B.P. M.P. Dimethone DimethoneQC QC QC anhydride

QC

Benzaldehyde 179 195 200Phenylacetaldehyde 194 34 165 126Salicylaldehyde (1) 197 208m-Tolualdehyde 199 172 2060-Tol ualdehyde 200 167 215p-Tol ualdehyde 204Phenoxyacetaldehyde 215d 383-Phenylpropanal 224m-Methoxybenzaldehyde 230Cuminaldehyde (2) 235 171 173Anisaldehyde (3) 248 2 145 243Cinnamaldehyde 252 213 1751-Naphthaldehyde 292 34Piperonal (4) 263 37 178 2200-Methoxybenzaldehyde 236 382,3-Dimethoxybenzaldehyde 54Veratraldehyde (5) 285 582-Na phthaldehyde 612,4-Dimethoxybenzaldehyde 69Vanillin (6) 81 197 228m-Hydroxybenzaldehyde 240 108p-Hydroxybenzaldehyde 116 189 246Terephthaldialdehyde 246 116{J-Resorcylaldehyde (7) 136Protocatechuicaldehyde (8) 153 145

Haloqeno-aldehydes

o-Chlorobenzaldehyde 213 11 205 225m-Chlorobenzaldehyde 214 18o-Bromobenzaldehyde 230 22m-Bromobenzaldehyde 234o-Iodobenzaldehyde 373,4-Dichlorobenzaldehyde 248 44p-Chlorobenzaldehyde 214 47m-Iodobenzaldehyde 57p-Bromobenzaldehyde 672,6-Dichlorobenzaldehyde 712,4-Dichlorobenzaldehyde 72p-Iodobenzaldehyde 78

Nitro- and amino-aldehydes

o-Aminobenzaldehyde 40o-Nitrobenzaldehyde 44m-Nitrobenzaldehyde 58p-Aminobenzaldehyde 72p-Dimethylaminobenzaldehyde 74P:Nitrobenzaldehyde 106m-Aminobenzaldehyde Amorphous

(I) o-Hydroxybenzaldehyde.(2) p-Isopropylbenzaldehyde.(3) p-Methoxybenzaldehyde.(4) 3,4-Methylenedioxybenzaldehyde.

1334


2,4-Dinitrophenyl Semicarbazone Oxime Phenylhydrazone p-Nitrophenylhydrazone QC QC QC hydrazoneQC QC

237 224 35d 158 192121 156 99 63 151252 231 63 143 228194 223 60 91 157194 212 49 106 222233 234 80 112 201

145 95 86149 127 94 123

40 171241 211 52 129 190254 209 132(65) 121 161255d 215 139 168 195

221 98 80 234265 234 110 106 200253 215 92 205

231 99 138264 177 95 121270 245 156 206 230

106269 239 117 105 228259 198 90 130 222280 224 72 178 266

200 278d 281286 260 192 160 285275 230 157 176

209 229 (146) 76d 86 249248 229 7ld 134 216

214 102 240205 72d 141 220206 108 79

119 277265 232 107 (140) 127 220

226 62 155 212228 111 113 208

150

224 121 201

247 135 221 220265 256 103 156 263292 246 122 121 247

173 124 156325 222 185 148 182320 221 133 159 249

280d 195 162 226

(5) 3,4-Dimethoxybenzaldehyde.(6) 4-Hydroxy-3-methoxybenzaldehyde.(7) 2,4-Dihydroxybenzaldehyde.(8) 3,4-Dihydroxybenza1dehyde.

1335


Table 10.17 AIiphatic ketones

Ketone B.P.QC

M.P.QC

2,4-Dinitro-phenylhydrazoneQC

Acetone 56Ethyl methyl ketone (butan-2-one) 80Methyl vinyl ketone (but-3-en-2-one) 80Biacetyl (butane-2,3-dione) 88Isopropyl methyl ketone (3-methylbutan-2-one) 94Methyl propyl ketone (pentan-2-one) 102Diethyl ketone (pentan-3-one) 102Pinacolone (t-butyl methyl ketone) 106Isobutyl methyl ketone (4-methylpentan-2-one) 117Di-isopropyl ketone (2,4-dimethylpentan-3-one) 124Ethyl propyl ketone (hexan-3-one) 124Butyl methyl ketone (hexan-2-one) 1284-Methylpent-3-en-2-one 130Cyclopentanone 131Pentane-2,4-dione 1392-Methylcyclopentanone 139Dipropyl ketone (heptan-t-one) 144Acetyl methyl carbinol (3-hydroxybutan-2-one) 145Acetol (hydroxyacetone) 146Heptan-z-one 151Cyclohexanone 1562-Methylcyclohexanone 1654-Hydroxy-4-methylpentan-2-one 166Di-isobutyl ketone (2,6-dimethylheptan-4-one) 168Methyl acetoacetate 1703-Methylcyclohexanone 1704-Methylcyclohexanone 171Hexyl methyl ketone (octan-2-one) 173Cycloheptanone 180Cyclohexyl methyl ketone 180Ethyl acetoacetate (ethyl 3-oxobutanoate) 181Dibutyl ketone (nonan-c-one) 188(+ j-Fenchone 193Hexane-2,5-dione 194Methyllevulinate (methyI4-oxopentanoate) 196Phorone (1) 199{J-Thujone 202Ethyl1evulinate 206( - )-Menthone 209Isophorone (2) 215Pulegone 224Undecan-S-one 226(+ )-Carvone 230Tridecan-7-one 255ex-Ionone 130/13{J-Ionone 139/182,2'-Furoin2,2'-Furil(+ )-Camphor 209

28

14

33

135165179

128115

315 (Di)1201441561259588

130107203146209

7531812989

16213720392

15513458

14814093

140257 (Di)142118114102146130147

191

151128217215177

ChloroacetoneLl-Dichloroacetone1,3-Dichloroacetone

119120173 45

125

133

1336(1) 2,6-Dimethylhepta-2,5-dien-4-one. (2) 3,3,5-Trimethylcyclohex-z-enone.


Table 10.18 Aromatic ketones

Ketone B.P. M.P. 2,4-Dinitro-QC QC phenylhydrazooe

QC

Acetophenone 202 20 250 (237)2-Hydroxyacetophenone 2152-Methylacetophenone (1) 216 159Benzyl methyl ketone 216 27 156Propiophenone (2) 218 19 1913-Methylacetophenone (3) 220 207Isobutyrophenone (4) 222 1634-Methylacetophenone (5) 224 28 258Benzyl ethyl ketone 226Butyrophenone (6) 230 12 190m-Methoxyacetophenone 240Valerophenone (7) 242 166o-Methoxyacetophenone 245cx-Tetralone 129/12 257{J-Tetralone 138/16 18l-Acetylnaphthalene 302 34Phenyl o-tolyl ketone (8) 310 190Phenyl m-tolyl ketone 314 221Dibenzyl ketone 331 35 100p-Methoxyacetophenone 258 39 220e-Hydrindone 242 42 258Benzalacetone 262 42 227Benzophenone 306 49 2382-Acetylnaphthalene 301 56 262Phenyl styryl ketone (9) 347 58 245Phenyl p-tolyl ketone 326 60 200Deoxybenzoin (10) 320 60 206p-Methoxybenzophenone 355 62 180Fluorenone (11) 341 83 284e-Hydroxyacetophenone (12) 86Di-p-tolyl ketone 335 95 229Benzil 347d 95 189m-Hydroxyacetophenone 96p-Hydroxyacetophenone 109 261Dibenzylideneacetone 112 180p-Benzoquinone 116 186Acenaphthenone 1211,4-Naphthoquinone 125Benzoin 344 137 2451,2-Naphthoquinone 146Resacetophenone (13) 1479,10-Phenanthraquinone 207 313Phloroacetophenone (14) 219Anthraquinone 285

Haloqeno-ketones

m-Chloroacetophenone 228o-Chloroacetophenone 229 206p-Chloroacetophenone 236 20 231o-Bromoacetophenone 112/10m-Bromoacetophenone 131/16 8-Bromoacetophenone (15) 51p-Bromoacetophenone 256 51 230p-Chlorobenzophenone 323 78 185

TABLES OF DERiVATIVES 10

10 PHYSICAL CONSTANTS Of ORGANIC COMPOUNDS

Table 10.18 Aromatic ketones (continued)

Ketone

Haloqeno-ketones (continued)

B.P.QC

M.P.QC

2,4-Dinitro-phenylhydrazoneQC

p- Bromobenzophenonep-Iodoacetophenoneex,p-Dibromoacetophenone (16)

Nitro- and amino-ketones

o-Nitroacetophenoneo-Aminoacetophenonem-Nitroacetophenonep-Nitroacetophenonem-Aminoacetophenonep-Aminoacetophenone

(1) Methyl o-tolyl ketone.(2) Ethyl phenyl ketone.(3) Methyl m-tolyl ketone.(4) Isopropyl phenyl ketone.(5) Methyl p-tolyl ketone.(6) Phenyl propyl ketone.(7) Butyl phenyl ketone.(8) 2-Methylbenzophenone.

1340

350 82 23085

109

159/16251 20

81 2288199

294 106

Semi-carbazone

290257

196250

OximeQC

169

115

109132

148

Phenyl-hydrazoneQC

126

108135132

p-Nitro-phenyl-hydrazoneQC


Other derivatives QC

(9) Chalcone.(10) Benzyl phenyl ketone.(11) Diphenylene ketone.(12) Phenacyl alcohol.(13) 2,4-Dihydroxyacetophenone.(14) 2,4,6-Trihydroxyacetophenone.(15) Phenacyl bromide.(16) p-Bromophenacyl bromide.

1341


Table 10.19 Quinones

Quinone SemicarbazoneQC

OximeQC

Thymoquinone 45 204 1622-Methyl-1,4-benzoquinone 69 179 1352-Methyl-I ,4-naphthoq uinone 106 247 167Duroquinone (1) 112p- Benzoquinone 116 243d 240dlA-Naphthoquinone 125 247 1981,2-Naphthoquinone 116-120 184 1621-Methylanthraquinone 1722-Methylanthraquinone 1773-Methyl-1,2-benzoquinone 195 140Camphorquinone 199 236 170Quinizarin (2) 2019,10-Phenanthraquinone 206 220d 162Acenaphthenequinone 261 192 222 DiAnthraquinone 286 224Chloranil (3) 290*Alizarin 290

* Sealed tube. (1) 2,3,5,6-Tetramethyl-I ,4-benzoquinone.

Table 10.20 Aliphatic carboxylic acids

Acid RP. M.P. Anilide p-Tolu- AmideQC QC QC idide QC

QC

Formic 101 8 50 53 3Acetic 118 16 114 153 82Acrylic (propenoic) 140 13 105 141 85Propionic (propanoic) 141 106 126 79Propiolic (propynoic) 144d 18 87 62Isobutyric (2-methylpropanoic) 154 105 109 129Butyric (butanoic) 163 96 75 115Pivalic (2,2-dimethylpropanoic) 164 34 133 120 154Pyruvic (2-oxopropanoic) 165d 13 104 130 125Crotonic (cis) (but-2-enoic) 165 15 102 102Isovaleric (3-methylbutanoic) 176 110 109 1362-Methylbutanoic 177 112 93 112Valeric (pentanoic) 186 63 74 1062-Ethylbutanoic 193 127 116 1124-Methylpentanoic 199 112 63 121Methoxyacetic 203 58 96Hexanoic 205 74 100Ethoxyacetic 207 95 82Heptanoic 223 71 80 962-Ethylhexanoic 228 103Cyclohexanecarboxylic 233 31 144 186Octanoic 239 16 57 70 107Levulinic (4-oxopentanoic) 246 33 102 109 108

1342


p-Bromo- p-Nitro- p-Phenyl S-Benzyl- p-Bromo- Hydrazide* N-Benzyl-phenacyl benzyl phenacyl thlouron- anilide QC amide*ester ester ester ium salt QC QCQC QC QC QC

140 31 74 151 119 54 6086 78 111 136 166 77 61

63 31 102 152 148 40 44

77 89 149 151 104 8763 35 82 149 111 44 3876

68 78 159 129 68 545575 63 156 106 42

7777 70

72 70 159 105 5310472 62 95

54

67 67 157 10284 61

1343


Table 10.20 Aliphatic carboxylic acids (continued)

Acid B.P. M.P. Anilide p-Tolu- AmideQC QC QC idide QC

QC

Nonanoic 254 12 57 84 99Decanoic 269 31 70 78 108Undec-l O-enoic 275 25 67 68 87Undecanoic 164/15 29 71 80 103( j-Lactic (2-hydroxypropanoic) 122/15 18 59 107 79Dodecanoic 225/100 43 78 87 99Myristic (tetradecanoic) 250/100 58 84 93 103Palmitic (hexadecanoic) 268/100 63 91 98 106Oleic (cis-octadec-9-enoic) 233/10 16 41 43 76Cyanoacetic 66 198 120Stearic (octadecanoic) 291/100 70 94 102 109Crotonic (trans) (but-Z-enoic) 189 72 118 132 160Glycollic (hydroxyacetic) 79 97 143 120Citraconic (cis-methylbutenedioic) 93 175 186Glutaric (pentanedioic) 98 224 218 175Citric (hydrated) 100 199 189 215(- j-Malic (, m.p. 133 QC) 101 197 207 157Oxalic (dihydrate) 101 246 268 419dPimelic (heptanedioic) 105 156 206Azelaic (nonanedioic) 106 187 202 172Sebacic (decanedioic) 133 202 201 209Sorbic (hexa-2,4-dienoic) 134 153Furoic 134 124 108 142Maleic 135 187 142 181Malonic 135d 225 253 170meso-Tartaric 140 1902-Furylacrylic 141 169Suberic (octanedioic) 142 187 219 217Adipic (hexanedioic) 152 239 241 220Itaconic (methylenesuccinic) 165 190 192(+)-Tartaric 170 264 196Succinic 185 230 255 260(+ )-Camphoric 187 226 193Aconitic (trans-propene-l,2,3-

tricarboxylic) 191 250Mesaconic (trans-

methylbu tenedioic) 204 186 212 176()-Tartaric 206 226n-Galactaric 214Fumaric 286 314 266Thioacetic 93 76 131 115

Haloqeno-acids

2-Chloropropanoic 186 92 124 80Dichloroacetic 194 10 119 153 972-Bromopropanoic 206 25 99 125 123Bromoacetic 208 50 130 91 91Trichloroacetic 196 58 95 113 141Chloroacetic 189 63 137 162 120Iodoacetic 84 144 95Fluoroacetic 167 35 108Difluoroacetic 134 52Trifluoroacetic 72

1344

99

10580

116

178

148160

TABLES OF DERIVATIVES 1D

* See Section 9.6.17 for details of the preparation of hydrazides and N-benzylamides. 1345


Table 10.21 Aromatic carboxylic acids

Acid M.P.QC

AnilideQC

p- Toluidlde AmideQC QC

o-Ethoxybenzoic 25 1323-Phenylpropanoic (1) 48 98 135 105Phenylacetic 76 118 136 157Phenoxyacetic 99 101 1010-Methoxybenzoic 101 131 129o-Toluic 105 125 144 143m-Methoxybenzoic 110m-Toluic 111 126 118 95()-Mandelic (2) 120 152 172 134Benzylmalonic 120d 217 225Benzoic 121 162 158 1290-Benzoylbenzoic 128 195 165Cinnamic 133 153 168 147l-Naphthylacetic 133 156 181Acetylsalicylic 135 136 138Phenylpropiolic 136 126 142 109m-Ethoxybenzoic 137 1392-Naphthylacetic 142 200Diphenylacetic 148 180 173 168Benzilic 150 175 190 1552-Hydroxy-5-methylbenzoic (3) 153 178Salicylic 158 135 156 139l-Naphthoic 162 163 2022-Hydroxy-3-methylbenzoic (4) 169 1122-Hydroxy-4-methylbenzoic (5) 177p-Toluic 178 146 160 159p-Methoxybenzoic (6) 184 169 186 1622-Naphthoic 185 170 191 192p-Ethoxybenzoic 198 170 2023,4-Dihydroxybenzoic (7) 199d 167 2123-Hydroxybenzoic 201 157 163 167Phthalic (benzene-l,2-dicarboxylic) c. 208d 251 2194-Hydroxy-3-methoxy benzoic (8) 2104-Hydroxybenzoic 213 197 204 1622,4-Dihydroxybenzoic (9) 213 127 2213-Hydroxy-2-naphthoic 223 244 222 218l-Hydroxy-Z-naphthoic 226 218Diphenic 229 230 2123,4-Methylenedioxybenzoic (10) 229 169Gallic (3,4,5-trihydroxybenzoic) c. 240d 207 245Isophthalic (benzene-l,3-dicarboxylic) 347 280Terephthalic (benzene-l,4-dicarboxylic) sub. >300 337Benzene-Lf.Svtricarboxylic (11) 380 365

Haloqeno-carboxylic acids

m-Chlorophenoxyacetic 100m-Fluorobenzoic 124 1300-Flu orobenzoic 127 116o-Chlorobenzoic 141 118 131 141o-Chlorophenoxyacetic 146 121 150o-Bromobenzoic 150 141 155m-Bromobenzoic 155 146 155

1346

107

102126

106

110105

123

98155

171168

Hydrazide, 139Hydrazide, 73Hydrazide, 110

TABLES OF DERIVATIVES 1D

1347


Table 10.21 Aromatic carboxylic acids (continued)

Acid M.P.QC

AnilideQC

p- ToluidideQC

AmideQC

1348

Haloqeno-carboxylic acids (cont inued)

p-Chlorophenoxyacetic 157 125 133m-Chlorobenzoic 158 124 134o-Iodobenzoic 162 141 1842,4-Dichl orobenzoic 164 194p-Fluorobenzoic 185 154m-Iodobenzoic 187 1863,4-Dichlorobenzoic 209 169p-Chlorobenzoic 243 194 179p-Bromobenzoic 252 197 189p-Iodobenzoic 270 210 218

Nitro- and amino-carboxylic acids

m-Nitrophenylacetic 120 110m-Nitrobenzoic 141 154 162 1420-Nitrophenylacetic 141 161Anthranilic (o-aminobenzoic) 146 131 151 109

o-Nitrobenzoic 147 155 175p-Nitrophenylacetic 152 212 210 1984-Nitrophthalic 165 200m-Aminobenzoic 174 140 1112,4-Dinitrobenzoic 183 204N-Acetylanthranilic 185 167 171Hippuric (12) 187 208 183p-Aminobenzoic 188 114m-Nitrocinnamic 205 1963,5-Dinitrobenzoic 207 234 1833-Nitrophthalic 219 234 223 2012,4,6-Trinitrobenzoic 228 264Nicotinic 235 85 150 128p-Nitrobenzoic 239 211 203 201o-Nitrocinnamic 240 185{J-Phenylalanine (13) 273 140p-Nitrocinnamic 287 217

(I) Hydrocinnamic acid.(2) 2-Hydroxy-2-phenylacetic acid.(3) 6-Hydroxy-m-toluic acid.(4) 2-Hydroxy-m-toluic acid.(5) 2-Hydroxy-p-toluic acid.(6) Anisic acid.(7) Protocatechuic acid.


1349


Table 10.22 Acid chlorides (aIiphatic)

Acyl chloride B.P. QC M.P. QC tlfJ" nil'"(JmmHg)

Acetyl 52 1.104 1.390Propionyl (propanoyl) 80 1.056 1.404Isobutyrl (2-methylpropanoyl) 92 1.017 1.408Butyryl (butanoyl) 102 1.028 1.412Chloroacetyl 105 1.420 1.454Dichloroacetyl 108Methoxyacetyl 113 1.187 1.4193-Methylbutanoyl 115 0.987 1.416Trichloroacetyl 118 1.620 1.470Crotonoyl 126Valeryl (pentanoyl) 127 1.000 1.4204-Methylpentanoyl 144 0.973Hexanoyl 152 0.975 1.426Heptanoyl 175 0.962 1.432Octanoyl 195 0.949 1.432

Nonanoyl 215 0.942 1.433Decanoyl 232Oxalyl 64 1.479 1.432Succinyl 192 17 1.375 1.468Glutaryl 218 1.324 1.473Adipoyl 125/11Pimeloyl 137/15Suberoyl 150/12 1.171 1.468Azelaoyl 165/13Sebacoyl 182/16 1.212 1.468

Table 10.23 Acid anhydrides (aIiphatic)

Anhydride B.P. QC M.P. QC tlfJ" n/r"(JmmHg)

Acetic 140 1.081 1.390Propionic 168 1.022 1.404Isobutyric 182 0.956Butyric 198 0.968 1.413Citraconic 213 7Isovaleric

(3-methylbutanoic) 215 0.933 1.404Valeric 218 0.9254-Methylpentanoic 139/19Hexanoic 245 0.920 1.430Crotonic 248 1.040 1.474Heptanoic 258 17 0.917 1.433Octanoic 285 0.910 1.434Maleic 198 56Glutaric 150/10 56Itaconic 139/30 68Succinic 261 120(+ )-Camphoric 270 221

Trifluoroacetic 39 1.490 1.269Dichloroacetic 101/16Trichloroacetic 223Chloroacetic 109/11 46

1350

Table 10.24 Acid chlorides and acid anhydrides ofaromatic acids

Acid chloride RP. QC M.P. QC(/mmHg)

Benzoyl 197Phenylacetyl 210o-Toluoyl 212m-Toluoyl 219p-Toluoyl 227m-Methoxybenzoyl 2440-Methoxybenzoyl 254Phthaloyl 281 16Anisoyl 145/14 24l-Naphthoyl 163/10 24Cinnamoyl 131/11 362-Naphthoyl 305 53Diphenylcarbamoyl 86

p-Chlorobenzoyl 222 16m-Chlorobenzoyl 225o-Chlorobenzoyl 238

m-Bromobenzoyl 2430-Bromobenzoyl 245 11p-Bromobenzoyl 245 42

0-Nitrobenzoyl 148/9 20m-Nitrobenzoyl 278 352,4-Dinitrobenzoyl 463,5-Dinitrobenzoyl 196/11 74p-Nitrobenzoyl 753-Nitrophthaloyl 77

Anhydride RP. QC M.P.QC

o-Toluic 39Benzoic 360 42m-Toluic 71Phenylacetic 72p-Toluic 95Anisic 99Phthalic 284 1322-Naphthoic 135Cinnamic 136l-Naphthoic 146Na phthalene-I ,2-dicarboxylic 169Diphenic 217(+ )-Camphoric 270 222Naphthalene-2,3-dicarboxylic 246dNaphthalene-lBsdicarboxylic 274

o-Chlorobenzoic 79m-Chlorobenzoic 95p-Chlorobenzoic 194Tetrachlorophthalic 255Tetrabromophthalic 280Tetra-iodophthalic 325

3.5-Dinitrobenzoic 1094-Nitrophthalic 1190-Nitrobenzoic 1352,4-Dinitrobenzoic 160m-Nitrobenzoic 1633-Nitrophthalic 164p-Nitrobenzoic 190 1351


Table 10.25 Aliphatic estersIt is considered that the table will be of greatest use if the esters are subdivided under the variousacids rather than arranged in order of increasing b.p. or m.p. irrespective of the nature of the carb-oxylic acid. The latter procedure leads to an unwieldy, heterogeneous table which has relatively littlepedagogic or, indeed, practical value.

Ester B.P. QC tilt'(JmmHg)

Methyl formate 32 0.974Ethyl formate 53 0.923Isopropyl formate 71 0.873Propyl formate 81 0.904t-Butyl formate 83Allyl formate 84 0.946s-Butyl formate 97 0.884Isobutyl formate 98 0.876Butyl formate 106 0.892Isopentyl formate 124 0.882Pentyl formate 131 0.885Cyclopentyl formate 138 1.000Hexyl formate 154 0.879Cyclohexyl formate 161 0.994Ethylene glycol diformate 177 1.229

Methyl acetate 56 0.939Ethyl acetate 77 0.901Isopropyl acetate 88 0.872t-Butyl acetate 97 0.867Propyl acetate 101 0.887Allyl acetate 104 0.928s-Butyl acetate 112 0.872Isobutyl acetate 116 0.871Butyl acetate 124 0.881t-Pentyl acetate 124 0.873Isopentyl acetate 141 0.872Pentyl acetate 148 0.875Cyclopentyl acetate 153 0.975Hexyl acetate 169 0.872Cyclohexyl acetate 172 0.970Heptyl acetate 192 0.865Tetrahydrofurfuryl acetate 195 1.061Octyl acetate 210

Methyl 'cellosolve' acetate 144 1.088'Cellosolve' acetate 156 0.976Ethylene glycol diacetate 190 1.104Propylene glycol diacetate 191 1.059Trimethylene glycol diacetate 210 1.069'Carbitol' acetate 217 1.013Butyl 'carbitol' acetate 246 0.983a-Monoacetin (glycerol l-acetate) 158/15 1.206Diacetin (mixture of ay and afJ) 143/12 1.180Triacetin (glyceryl triacetate) 153/22 1.161

Methyl propionate (propanoate) 79 0.915Ethyl propionate 98 0.892Isopropyl propionate 111Propyl propionate 122 0.882Allyl propionate 123 0.914

1352

nil'"

1.3441.3601.3681.377

1.3841.3861.3891.3981.4001.4321.4071.443

1.3621.3721.3771.3861.3841.4041.3891.3901.3941.3921.4001.4021.4321.4091.4421.4141.438

1.4151.417

1.416

1.430

1.3771.384

1.3931.410


Table 10.25 AIiphatic esters (continued)

Ester B.P. QC d'fl' nlr'(JrnrnHg)

Butyl propionate 145 0.875 1.401Isopentyl propionate 160 0.859 1.412Pentyl propionate 169 0.881Hexyl propionate 190 0.870 1.419

Methyl butyrate (butanoate) 102 0.898 1.387Ethyl butyrate 120 0.879 1.392Isopropyl butyrate 128Propyl butyrate 142 0.872 1.400Allyl butyrate 142 0.902 1.416Butyl butyrate 165 0.869 1.406Isopentyl butyrate 179 0.864 1.411Pentyl butyrate 185 0.866 1.412Hexyl butyrate 208 0.866 1.420

Methyl isobutyrate (2-rnethylpropanoate) 91 0.888 1.383Ethyl isobutyrate 110 0.869 1.387Isopropyl isobutyrate 121Propyl isobutyrate 134 0.864 1.396Butyl isobutyrate 156 0.862 1.402

Methyl valerate (pentanoate) 127 0.890 1.397Ethyl valera te 144 0.874 1.400Isopropyl valerate 154 0.858 1.401Propyl valerate 164 0.870 1.407Butyl valerate 184 0.868 1.412

Methyl isovalerate (3-rnethylbutanoate) 116 0.881 1.393Ethyl isovalerate 133 0.865 1.396Propyl isovalerate 156 0.862 1.403Isobutyl isovalerate 171 0.853 1.406Butyl isovalerate 176 0.861 1.409

Methyl hexanoate 149 0.885 1.405Ethyl hexanoate 168 0.871 1.407Propyl hexanoate 187 0.867 1.417Butyl hexanoate 208 0.865 1.421Pentyl hexanoate 226 0.863 1.426

Methyl cyclohexanecarboxylate 183 0.990 1.451Ethyl cyclohexanecarboxylate 196 0.962 1.448

Methyl heptanoate 171 0.882 1.412Ethyl heptanoate 186 0.870 1.413Propyl heptanoate 208 0.866 1.421Butyl heptanoate 226 0.864 1.426

Methyl octanoate 192 0.878 1.417Ethyl octanoate 206 0.869 1.418

Methyl nonanoate 214Ethyl nonanoate 227 0.866 1.422

Methyl decanoate 228 0.873 1.426Ethyl decanoate 242 0.865 1.426Propyl decanoate 115/5 0.862 1.428Butyl decanoate 123/4 0.861 1.430

1353



Ester B.P. QC d'fl' nlr'(JmmHg)

Methyl dodecanoate 262 0.870 1.432Ethyl dodecanoate 273 0.862 1.431Propyl dodecanoate 140/4 0.862 1.434Butyl dodecanoate 154/5 0.860 1.436

Methyl stearate m.p.39Ethyl stearate m.p.33

Methyl chloroformate 73 1.223 1.387Ethyl chloroformate 94 1.136 1.397Propyl chloroformate 115 1.090 1.404Isobutyl chloroformate 129 1.040 1.406Butyl chloroformate 138 1.079 1.412Pentyl chloroformate 61/15 1.417Hexyl chloroformate 63/10

Methyl chloroacetate 129 1.234 1.422Ethyl chloroacetate 142 1.150 1.422Methyl dichloroacetate 143 1.377 1.443Ethyl dichloroacetate 156 1.283 1.438Methyl trichloroacetate 152 1.488 1.457Ethyl trichloroacetate 164 1.380 1.450

Methyl bromoacetate 144dEthyl bromoacetate 169 1.506 1.451

Methyl iodoacetate 170Ethyl iodoacetate 180 1.818* 1.508*

Methyl methoxyacetate 130 1.051 1.396Ethyl methoxyacetate 132 1.007

Methyl ethoxyacetate 148 1.006Ethyl ethoxyacetate 158 0.970 1.403

Methyl acrylate 80 0.960 1.398Ethyl acrylate 101 0.909 1.406

Methyl crotonate 119 0.946 1.425Ethyl crotonate 137 0.918 1.425Propyl crotonate 157 0.908 1.428Butyl crotonate 55/4 0.899 1.432Isopentyl crotonate 60/4 0.891 1.434Pentyl crotonate 72/5 0.894 1.436

Methyl lactate 145 1.089 1.414Ethyl lactate 154 1.030 1.415

Methyl glycollate 151 1.166Ethyl glycollate 160 1.082

Methyl pyruvate 138Ethyl pyruvate 155 1.055 1.406

Methyl levulinate 196 1.049 1.423Ethyllevulinate 206 1.011 1.423

1354



Ester B.P. QC tP.,. nil'"(JmmHg)

Methyl furoate 181 1.180 1.486Ethyl furoate 197 (m.p. 34) 1.117* 1.480*

Trimethyl orthoformate 105 0.968 1.379Triethyl orthoformate 143 0.893 1.390Tripropyl orthoformate 91/17 0.879 1.407Tributyl orthoformate 127/16 0.871 1.416

Dimethyl carbonate 90 1.071 1.369Diethyl carbonate 126 0.976 1.384Dipropyl carbonate 165 0.943 1.400Diisobutyl carbonate 188 0.914 1.407Dibutyl carbonate 205 0.925 1.412

Dimethyl oxalate m.p.54Diethyl oxalate 183 1.079 1.410Diisopropyl oxalate 191 0.995 1.413Dipropyl oxalate 212 1.019 1.416Dibutyl oxalate 241 0.987 1.423Diisopentyl oxalate 127/7 0.961 1.427Dipentyl oxalate 139/9 0.966 1.429

Dimethyl malonate 179 1.119 1.420Diethyl malonate 197 1.055 1.414

Diallyl succinate 104 1.051 1.452Dimethyl succinate 195 1.120 1.420Diethyl succinate 218 1.042 1.420Diisopropyl succinate 82/3 0.985 1.418Dipropyl succinate 102/3 1.006 1.425Diisobutyl succinate 116/4 0.968 1.427Dibutyl succinate 120/3 0.977 1.430Diisopentyl succinate 130/4 0.958 1.434Dipentyl succinate 129/2 0.960 1.434

Dimethyl glutarate 109/21 1.087 1.424Diethyl glutarate 118/15 1.023 1.424

Dimethyl adipate 121/17 1.063 1.428Diethyl adipate 134/17 1.009 1.428Diisopropyl adipate 120/6 0.966 1.425Dipropyl adipate 146/9 0.981 1.431Dibutyl adipate 159/17 0.945 1.435Diisopentyl adipate 184/13 0.945 1.437Dipentyl adipate 186/10 0.948 1.439

Dimethyl pimelate 128/16 1.038 1.431Diethyl pimelate 149/18 0.993 1.430

Dimethyl suberate 120/6 1.024 1.434Diethyl suberate 131/5 0.981 1.432Dipropyl suberate 165/8 0.962 1.435Dibutyl suberate 176/4 0.948 1.439

* Values at 21 QC with supercooled liquid.

1355



Ester B.P. QC M.P. QC d3.'" nil'"(JmmHg)

Dimethyl azelate 156/20 1.007 1.436Diethy1 azelate 291 0.973 1.435

Dimethyl sebacate 293 27Diethyl sebacate 307 0.964 1.437Dipropyl sebacate 179/5 0.950 1.439

Dimethyl maleate 201 1.150 1.442Diethyl maleate 220 1.066 1.440Dipropyl maleate 126/12 1.025 1.443Dibutyl maleate 147/12 0.994 1.445

Dimethyl fumarate 193 102Diethyl fumarate 214 1.052 1.441Dipropyl fumarate 110/5 1.0l3 1.444Dibutyl fumarate 139/5 0.987 1.447

Dimethyl itaconate 208 38Diethyl itaconate 229 1.047 1.439

Dimethyl mesaconate 205 1.120 1.454Diethyl mesaconate 225 1.043 1.448

Dimethyl citraconate 210 1.112 1.448Diethy1 citraconate 228 1.041 1.444

Dimethyl ( + )-tartrate 280 61Diethyl (+ j-tartrate 280 18 1.203 1.447Dipropyl ( + j-tartrate 297 1.139Dibutyl ( + j-tartrate 200/18 22

Dimethyl ( )-tartrate 282 90Diethyl ( j-tartrate 280 18 1.203 1.447Dipropyl ( )-tartrate 286 25Dibutyl ( j-tartrate 320 1.086

Dimethyl malate 242 1.233 1.442Diethyl malate 253 1.129 1.436

Dimethyl galacturate 167Diethyl galacturate 164

Trimethyl citrate 76Triethyl citrate 294 1.137 1.466

1356


Table 10.26 Aromatic esters

It is considered that the table will be of greatest use if the esters are in the main subdivided under thevarious acids rather than be arranged in order of increasing b.p. or m.p. irrespective of the nature ofthe carboxylic acid. The latter procedure leads to an unwieldy, heterogeneous table which has relat-ively little pedagogic or, indeed, practical value.

Ester B.P. QC M.P. QC div' ""no(/mmHg)

Methyl benzoate 199 1.089 1.517Ethyl benzoate 212 1.047 1.505Isopropyl benzoate 218 1.015 1.491Propyl benzoate 230 1.023 1.500Allyl benzoate 230 1.052Isobutyl benzoate 242 0.997Butyl benzoate 248 1.005 1.497Isopentyl benzoate 262 0.986 1.495Pentyl benzoate 137/15Ethylene glycol dibenzoate 73

Methyl phenylacetate 215 1.068 1.507Ethyl phenylacetate 228 1.033 1.497Propyl phenyl acetate 241 1.010 1.493Butyl phenylacetate 256 0.994 1.489

Methyl o-toluate 213 1.068Ethyl o-toluate 227 1.034 1.508Methyl m-toluate 215 1.061Ethyl m-toluate 227 1.028 1.506Methyl p-toluate 217 34Ethyl p-toluate 228 1.025 1.507

Methyl salicylate 223 1.184 1.537Ethyl salicylate 234 1.125 1.522Propyl salicylate 240 1.098 1.516Butyl salicylate 260 1.073 1.512Methyl m-hydroxybenzoate 70Ethyl m-hydroxybenzoate 295 73Ethyl p-hydroxybenzoate 297 116Methyl p-hydroxybenzoate 131

Methyl o-methoxybenzoate 248 1.156 1.534Ethyl o-methoxybenzoate 261 1.104 1.525Methyl m-methoxybenzoate 237 1.131 1.522Ethyl m-methoxybenzoate 251 1.100 1.515Methyl anisate 255 49Ethyl anisate 269 7 1.103 1.524

Methyl o-chlorobenzoate 234 1.536Ethyl o-chlorobenzoate 243 1.190 1.522Methyl m-chlorobenzoate 231 20 1.492Ethyl m-chlorobenzoate 242 1.182 1.520Ethyl p-chlorobenzoate 238 1.181 1.524Methyl p-chlorobenzoate 44

Methyl o-brornobenzoate 246Ethyl o-bromobenzoate 255Ethyl m-bromobenzoate 259Methyl m-bromobenzoate 32Ethyl p-bromobenzoate 263Methyl p-bromobenzoate 81

1357


Table 10.26 Aromatic esters (continued)

Ester B.P. QC M.P. QC d'fl' nlr'(JmmHg)

Ethyl o-iodobenzoate 275Methyl o-iodobenzoate 278Ethyl m-iodobenzoate 150/15Methyl m-iodobenzoate 277 54Ethyl p-iodobenzoate 153/14Methyl p-iodobenzoate 114

Ethyl o-nitrobenzoate 30Methyl o-nitrobenzoate 275 1.286Ethyl m-nitrobenzoate 297 47Methyl m-nitrobenzoate 279 79Ethyl p-nitrobenzoate 57Methyl p-nitrobenzoate 96

Ethyl 3,5-dinitrobenzoate 94Methyl 3,5-dinitrobenzoate 108Ethyl 2,4-dinitrobenzoate 41Methyl 2,4-dinitrobenzoate 70

Ethyl anthranilate 267 13 1.117 1.565Methyl anthranilate 300 24Ethyl m-aminobenzoate 294Methyl m-aminobenzoate 38Ethyl p-aminobenzoate 92Methyl p-aminobenzoate 112

Ethyl cinnamate 273 1.049 1.560Propyl cinnarnate 284 1.028 1.551Butyl cinnamate 162/12 1.013 1.544Methyl cinnamate 261 36

Methyl hydrocinnamate 232 1.043 1.503Ethyl hydrocinnamate 248 1.016 1.495Propyl hydrocinnamate 262 0.998 1.491Butyl hydrocinnamate 123/11 0.984 1.489

Ethyl o-nitrocinnamate 44Methyl o-nitrocinnamate 73Ethyl m-nitrocinnamate 79Methyl m-nitrocinnamate 124Ethyl p-nitrocinnamate 142Methyl p-nitrocinnamate 161

Methyl o-aminocinnamate 65Ethyl o-aminocinnamate 78Ethyl m-aminocinnamate 64Methyl m-aminocinnamate 84Ethyl p-aminocinnamate 69Methyl p-aminocinnamate 129

Methyl phenoxyacetate 245 1.147Ethyl phenoxyacetate 251 1.101Ethyl ( j-mandelate 255 37Methyl ( j-mandelate 58

Methyl o-benzoylbenzoate 352 52Ethyl o-benzoylbenzoate 58

/

1358



Ester B.P. QC M.P. QC dlf" nlr"(JmmHg)

Ethyl diphenylacetate 58Methyl diphenylacetate 60

Dimethyl phthalate 282 1.191 1.516Diethyl phthalate 298 1.118 1.502Dipropyl phthalate 130/1Diisopropyl phthalate 154/10Dibutyl phthalate 205/20Diethyl isophthalate 285 11 1.121 1.507Dimethyl isophthalate 68Diethyl terephthalate 302 44Dimethyl terephthalate 142

Diethyl 3-nitrophthalate 45Dimethyl 3-nitrophthalate 69Diethyl 4-nitrophthalate 34Dimethyl 4-nitrophthalate 66

Methyl l-naphthoate 116/1 1.163 1.612Ethyl I-naphthoate 309 1.121 1.594Ethyl 2-naphthoate 304 32Methyl 2-naphthoate 290 77

Diethyl diphenate 42Dimethyl diphenate 74

Furfuryl acetate 176 1.118

Phenyl acetate 196 1.078 1.503Phenyl propanoate 211 20 1.050Phenyl butanoate 228 1.023Diphenyl oxalate 190/15Phenyl salicylate (salol) 43

Diphenyl succinate 330 121Phenyl benzoate 299 68Phenyl cinnamate 73Diphenyl carbonate 306 78

o-Cresyl acetate 208 1.045p-Cresyl acetate 212 1.050 1.500m-Cresy I aceta te 212 12 1.043 1.498Guaiacol acetate 240 1.133 1.512Thymyl acetate 243Carvacryl acetate 245 0.994Resorcinol diacetate 278Eugenol acetate 282 30I-Naphthyl acetate 49Catechol diacetate 632-Naphthyl acetate 70Benzoin acetate 83Phloroglucinol triacetate 104Hydroquinone diacetate 124Pyrogallol triacetate 165

1359

10 PHYSICAL CONSTAITS OF ORGANIC COMPOUNDS


Ester B.P. QC M.P. QC tPov nil'"(JmmHg)

o-Cresyl benzoate 307Thymyl benzoate 33m-Cresyl benzoate 54l-Naphthyl benzoate 56p-Cresyl benzoa te 316 72Catechol dibenzoate 84Pyrogallol tribenzoate 902-Naphthyl benzoate 107Resorcinol dibenzoate 117Phloroglucinol tribenzoate 185Hydroquinone dibenzoate 199

Di-o-cresyl carbonate 60Diphenyl carbonate 306 78Diguaiacol carbonate 87Di-m-cresyl carbonate 111Di-p-cresyl carbonate 115

Benzyl formate 203 1.082Benzyl acetate 214 1.057 1.523Benzyl salicylate 186/10 1.180 1.581Benzyl benzoate 323 21Dibenzyl succinate 45

1-Phenylethyl acetate 2222-Phenylethyl acetate 224 1.059 1.512

1360


Table 10.27 Primary aIiphatic amides

Amide M.P. QC Xanthylamide QC

Formamide 2 184(b.p. 193d)

Propionamide 79 214Acetamide 82 245Acrylamide 86Heptanamide 96 154Dichloroacetamide 98Lauramide 99Hexanamide 101 160Myristamide 103Palmitamide 106 142Valeramide 106 167Octanamide 107 148Decanamide 108Stearamide 109 141Butyramide 115 187Chloroacetamide 120 209Cyanoacetamide 120 223Isobutyramide 129 211Isovaleramide 136 183Trichloroacetamide 141Furoamide 142 210Trimethylacetamide 154Cyclohexanecarboxamide 185

N-Allylurea 80N-Methylurea 102 230Urea 132 274N,N-Dimethylurea 182 250N-Acetylurea 218Thiourea 182

Ethyl carbamate (urethan) 49 169Methyl carbamate 54 193Butyl carbamate 54Isobutyl carbamate 55Pentyl carbamate 57Propyl carbamate 61Isopentyl carbamate 67Isopropyl carbamate 92

Malonamide 170 270Azelamide 172Glutaramide 175Maleamide 180Sebacamide 209Suberamide 217Adipamide 220()-Tartaramide 226Succinamide 260d 275Oxamide 419dSuccinimide 126 246

1361


Table 10.28 Primary aromatic amides

Amide M.P. QC Xanthylamide QC

2-Phenylpropanamide 92 158m-Toluamide 953-Phenylpropanamide 105 189Hydrobenzamide 110Benzamide 129 2240-Methoxybenzamide 129()-Mandelamide 133m-Chlorobenzamide 134Salicylamide 139o-Chlorobenzamide 141N-m- Tolylurea 142m-Nitrobenzamide 142o-Toluamide 143 200N-Phenylurea 147 225Cinnamamide 148N-Benzylurea 1490-Bromobenzamide 155m-Bromobenzamide 155Phenylacetamide 157 196p-Toluamide 159 225p-Hydroxybenzamide 162Anisamide 162Diphenylacetamide 167m-Hydroxybenzamide 167Piperonylamide 169p-Phenetylurea (N -p-ethoxyphenylurea) 1730-Nitrobenzamide 175p-Chlorobenzamide 179N-p-Tolylurea 1833,5-Dinitrobenzamide 183o-Iodobenzamide 184m-Iodobenzamide 186N,N-Diphenylurea 189 180p-Bromobenzamide 189N-o-Tolylurea 191 2282-Naphthamide 192p-Nitrobenzamide 201 232l-Naphthamide 202p-Ethoxybenzamide 202p-Iodobenzamide 218Phthalamide 219dPhthalimide 235 177

1363


Table 10.29 Substituted aromatic amides

Amide M.P. Amide M.P.C C

Formanilide 50 N-Propylacetanilide 50Nonananilide 57 N -Ethylacetanilide 54Octananilide 57 m-Chloroacetanilide 79Lactanilide 59 m-Methoxyacetanilide 80Valeranilide 63 o-Chloroacetanilide 88Decananilide 70 m-Bromoacetanilide 88Heptananilide 71 o-Methoxyacetanilide 88Lauranilide 78 m-Aminoacetanilide 88Myristanilide 84 0-Nitroacetanilide 94Acetoacetanilide 85 o-Bromoacetanilide 99Palmi tanilide 91 N-Methylacetanilide 103Stearanilide 94 o-Iodoacetanilide 110Hexananilide 95 Acetanilide 114Butyranilide 96 N -Ethyl-p-nitroacetanilide 118Isobutyranilide 105 Phenylacetanilide 118Acrylanilide 105 m-Iodoacetanilide 119Propionanilide 106 p- Methoxyacetanilide 130Isovaleranilide 110 o-Aminoacetanilide 132Acetanilide 114 2,4-Dimethylacetani lide 133Furoanilide 124 2,5-Dimethylacetanilide 1420-Toluanilide 125 4-Methyl-3-nitroacetanilide 148m-Toluanilide 126 m-Hydroxyacetanilide 1490-Methoxybenzanilide 131 N -Methyl-p-nitroacetanilide 153Salicylanilide 135 m-Nitroacetanilide 155p-Toluanilide 146 p-Aminoacetanilide 163Cinnamanilide 153 p-Bromoacetanilide 167m-Nitrobenzanilide 154 p-Hydroxyacetanilide 168o-Nitrobenzanilide 155 p-Chloroacetanilide 179Benzanilide 162 p- Iodoacetanilide 1841-Naphthanilide 163 2-Methyl-4-nitroacetanilide 196Anisanilide 169 o-Hydroxyacetanilide 2092-Naphthanilide 171 p- Nitroacetanilide 216p-Nitrobenzanilide 211 p-Hydroxy-N-methylacetanilide 240

Pimelic dianilide 156 Acetyl-m-toluidine 66Suberic dianilide 187 Acetyl-o-phenetidine 79Maleic dianilide 187 Acetyl-m-anisidine 80Azelaic dianilide 187 Acetyl-o-anisidine 88Sebacic dianilide 202 Acetyl-m-phenetidine 96Glutaric dianilide 224 Acetyl-o-toluidine 112Malonic dianilide 225 Acetyl-p-anisidine 130Succinic dianilide 230 Acetyl-p-phenetidine (phenacetin) 137Adipic dianilide 239 Acetyl-p-toluidine 154Oxanilide 246 Acetyl-J-naphthylamine 160

1364

Table 10.29 Substituted aromatic amides (continued)

TABLES OfDERIVATlVES 10

Amide M.P. Amide M.P.C C

NN'-Diacetyl-o-phenylenediamine 186 Benzoylpiperidine 48NN'-Diacetyl-m-phenylenediamine 191 N-Phenylsuccinimide 156N N'-Diacetyl-p-phenylenediarnine 304 N -Phenylphthalimide 205

Phthalimide 235Benzoyl-o-anisidine 60 Triphenylguanidine 145Benzoyl-m-anisidine Diphenylguanidine 147Benzoyl-m-phenetidine 103 Saccharin 220Benzoyl-o-phenetidine 104Benzoyl-m-toluidine 125 N-Phenylurethane 53Benzoyl-o-toluidine 144 Ethyl oxanilate 67Benzoyl-p-anisidine 154Benzoyl-p-toluidine 158 N ,N'-Di-m-tolylurea 218Benzoyl-l-naphthylamine 161 N,N'-Diphenylurea (carbanilide) 238Benzoyl-p-phenetidine 173 N,N'-Di-o-tolylurea 250

N,N'-Di-p-tolylurea 268N,N'-Di-I-naphthylurea 297

NN'-Dibenzoyl-m-phenylenediamine 240NN'-Dibenzoyl-o-phenylenediamine 301 Ethylbutylbarbituric acid 125N N'-Dibenzoyl-p-phenylenediamine > 300 Ethylhexylbarbituric acid 127

Ethylisopentylbarbituric acid 154Acetyl-N -methyl-o-toluidine 56 Ethylphenylbarbituric acid 172Acetyl-N -methyl-m-toluidine 66 Diallylbarbituric acid 172Acetyl-N-methyl-p-toluidine 83 Diethylbarbituric acid 198Acetyl-N-methyl-I-naphthylamine 94 Ethylisopropylbarbituric acid 201

Barbituric acid 245N-Formyldiphenylamine 74N-Acetyldiphenylamine 101 Butyl oxamate 88N-Benzoyldiphenylamine 180 Ethyl oxamate 131

1365


Table 10.30 AIiphatic nitrites (cyanides)

Cyanide Nitrile B.P.OC(Jmm Hg)

Vinyl Acrylo- 78Methyl Aceto- 82Ethyl Propiono- 97Isopropyl Isobutyro- 108Propyl Butyro- 118Allyl Vinylaceto- 118Chloromethyl Chloroaceto- 127Isobutyl Isovalero- 131Butyl Valero- 141

Isopentyl 4-Methylpentane- 154

Pentyl Hexane- 162

Hexyl Heptane- 183Heptyl Octane- 199Octyl Nonane- 224Nonyl Decane- 244Decyl Undecane- 254Undecyl Dodecane- 275Methylene Malono- 220 (I)Ethylene Succino- 276d (2)Trimethylene Glutaro- 286 (3)Tetramethylene Adipo- 295Pentamethylene Pimelo- 169/15Hexamethylene Subero- 185/15

Acetaldehyde cyanohydrin o-Hydroxypropiono- 183Ethylene cyanohydrin p-Hydroxypropiono- 221Trimethylene cyanohydrin y-Hydroxybutyro- 240Trimethylene chlorocyanide y-Chlorobutyro- 197Methyl cyanoacetate 200Ethyl cyanoacetate 2072-Furyl Furo- 147

Phenyl Benzo- 191Benzyl Phenylaceto- 109/15o-Tolyl o-Tolu- 205m-Tolyl m-To1u- 212

* Decomposition temperature. Sample placed in bath at 105-110C.t 15C.

1366


d10 nlf Acyl IX-Irninoalkyl-..phloroglucinol rnercaptoaceticcC acid

hydrochloride-cC

0.806 1.3910.784 1.344 218 1150.783 1.366 176 128

1370.791 1.384 181 1360.838 1.4061.1930.7880.799 1.397 149 138

(hydrate 88)0.803 1.406 122 128

(hydrate 104)0.805 1.407 121 136

(hydrate 96)0:810 1.4140.817t 1.422t0.822t0.829t 1.432t

0.827t

0.988 1.4290.962 1.4390.945 1.4410.933 1.445

0.988

1.0791.1011.063 1.4181.082 1.480

1.006 1.5281.016 1.523 1460.996 1.5301.032 1.525

(1) rn.p. 31 -c. (2) rn.p. 54 cc. (3) rn.p. 9 cc.

1367

Table 10.31 Aromatic nitrites

Nitrile B.P. QC M.P. QC

( )-Mandelonitrile 170d 22Benzonitrile 191o-Tolunitrile 205m-Tolunitrile 212{J- Phenylpropiononitrile 232Phenylacetonitrile 234y-Phenylpropiononitrile 261Cinnamonitrile 255 20p-T01unitrile 218 29m-Bromobenzonitrile 225 381-Naphthonitrile 299 36m-Chlorobenzonitrile 41o-Chlorobenzonitrile 232 43o-Bromobenzonitrile 252 53o-Iodobenzonitrile 552-Naphthonitrile 306 66p-Chlorobenzonitrile 223 96o-Nitrobenzonitrile 111p-Bromobenzonitrile 236 113p-Nitrophenylacetonitrile 116m-Nitrobenzonitrile 118Phthalonitrile 141p- Nitrobenzonitrile 149


1369


Table 10.32 Primary and secondary aIiphatic amines

Amine B.P. dl" nil'" Benzene-QC sulphonamide

QC

Methylamine -7 30Ethylamine 17 58Isopropylamine 35 0.689 1.374 26t-Butylamine 46Propylamine 49 0.717 1.388 36Allylamine 55 0.762 1.420 39s-Butylamine 63 0.725 1.393 70Isobutylamine 68 0.735 1.397 53Butylamine 77 0.741 1.401Isopentylamine 97 0.749 1.408Pentylamine 105 0.754 1.411Hexylamine 129 0.766 1.418 96Cyclohexylamine 134 0.867 1.459Heptylamine 155 0.775 1.425Ethanolamine 171 1.022 1.454Octylamine 177 0.782 1.429(- )-Menthylamine 212 0.854

Benzylamine 185 0.982 1.544 881-Phenylethylamine 1872-Phenylethylamine 198 0.854 69

1,2-Diaminoethane 117 (1) 0.898 1.457 1681,2-Diaminopropane 120 0.8741,3-Diaminopropane 136 0.889 1.4601,4-Diaminobutane 159 (2)1,5-Diaminopentane 180 1191,6-Diaminohexane 205 (3) 154

Dimethylamine 7 47Diethylamine 56 0.707 1.386 42Di-isopropylamine 84 0.717 1.392 94Dipropylamine 110 0.738 1.405 51Diallylamine 111Di-s-butylamine 135 0.753 1.411Di-isobutylamine 137 0.746 1.409Dibutylamine 159 0.760 1.418Di-isopentylamine 186 0.771 1.423Dipentylamine 205 0.777 1.427Dicyclohexylamine 255d (4)Diethanolamine (5) 270d (6) 1.097 1.478 130Pyrrolidine 89 0.854 1.424Piperidine 106 0.861 1.453 942-Methylpiperidine 1183-Methylpiperidine 1264-Methylpiperidine 128Morpholine 130 1.000 1.455 119Pyrrole 131 0.969 1.509Piperazine 140 (7) 292 (di)

1,2,3,4-Tetrahydroisoquinoline 232 1541,2,3,4-Tetrahydroquinoline 250 67

(m.p.20)

1370


Toluene-p- Phenyl- I-Naphthyl- Picrate N-Substi- Benzamide Acetamidesulphon- thiourea thiourea QC tuted phthal- QC QCamide QC QC imideQC QC

75 113 192 215 134 8063 106 121 165 78 7151 101 143 150 86 100

198 13452 63 103 135 66 8464 98 140 7055 101 140 7678 82 137 151 93 57

65 109 151 34 4265 102 97 138

69 103 13977 79 127 40

142 158 149 10475 121

160 127112

135 157 145

116 147 172 196 115 105 60189 120 57

66 135 174 130 116 114

160 102 233 244 172137 193 139250 148 101

224 168 255d 177 137148 135

220 158

79 135 168 158 4160 34 108 155 42

140161 75

86 123 59118

119 173 153 10399 110

123 11296 152 4855 135 45

138

147 136 148 7569d

173 280 196 144(mono) (di) (di)

195 129 4676

1371

10 PHYSICAL CONSTANTS OF ORGANIC COIPOUNOS

Table 10.32 Primary and secondary aIiphatic amines (continued)

Amine B.P. QC M.P. QC

Ester-amides (derivatives of aminoformic acid, NH 2COOH)

Methyl carbamateEthyl carbamate (urethan)Propyl carbamateButyl carbamatePentyl carbamateIsopentyl carbamateN-Methylurethan (Ethyl N-methyl carbamate)N-Ethylurethan (Ethyl N-ethyl carbamate)N -PropylurethanN-ButylurethanN-s-ButylurethanN-Phenylurethan (Ethyl N-phenyl carbamate)Ethyl oxanilate

177184195204d

170170192202194237

545061545767

5367

Note. Esters of carbamic acid upon boiling with aniline yield carbanilide (m.p. 238 QC), ammoniaand the corresponding alcohoL

Table 10.33 Primary aromatic amines*

Amine B.P. M.P. Acetamide Benzamide Benzene-QC QC QC QC QC sulphon-

amideQC

Aniline 183 114 163 112Benzylamine 185 60 105 88l-Phenylethylamine 187 57 1202-Phenylethylamine 198 51 116 690-Toluidine 200 112 144 124m-Toluidine 203 66 125 95p-Xylidine (I) 214 15 142 140p-Ethylaniline 215 94 151m-2-Xylidine (2) 215 11 177 168o-Ethylaniline 216 112 147m-4-Xylidine (3) 216 130 192 130m-5-Xylidine (4) 220 10 144 136o-Anisidine (5) 225 5 88 60 893,4-Dimethylaniline 226 49 99 118N,N-Methylphenylhydrazine 227 92 153 132o-Phenetidine (6) 229 79 104 102Mesidine (7) 232 216 206Phenylhydrazine 242 23 128 168m-Phenetidine 248 96 103m-Anisidine 251 80o-Aminoacetophenone 251d 20 77 98p-Phenetidine 254 135 173 143

* All aromatic amines should be treated as potentially carcinogenic (see Section 2.3.4, p. 49).

1372

0.981

(I) m.p. 8 QC.(2) m.p. 28 QC.(3) m.p. 42 QC.(4) m.p. 20 QC.

UBLES OF OERIVATIVES 10

Derivatives QC

N-p-Nitrobenzoyl, 152; Benzylidene, 179

1.422

N-Acetyl, 59; N-Benzoyl, 161; N-Nitroso, 62N-Acetyl, 65

(5) Di-2-hydroxyethylamine.(6) m.p. 28C.(7) m.p. 104QC; Hydrate, 6H 20 , m.p. 44 QC.

Toluene-p- Benzylidene Picrate 3-Nitro- 2,4-Dinitro- Formyl Phenylsulphon- derivative QC phthalimide phenyl derivative thioureaamide QC QC derivative QC QCQC QC

103 54 138 156 47 154116 199 143 156

167 135110 213 150 126 59 136114 200 130 161 104232 150

212 180 176 148

181 209 156 114 152209 77 153

127 200 185 151 83 136154

164 164 164 62 137167 193 193

145 172157 158 52 13868 169 158 138 57

148107 76 69 173 118 76 148

1373


Table 10.33 Primary aromatic amines (continued)


amideQC

Methyl anthranilate 255 24 101 100p-Aminodiethylaniline 261 104 172Ethyl anthranilate 266d 13 61 98 93Ethyl m-amino benzoate 294 114p-Aminodimethylaniline 262 41 132 228p-Toluidine 200 45 154 158 120o-Aminobiphenyl (8) 299 50 121 102l-Naphthylarnine C 300 50 160 161 169p-Aminobiphenyl (9) C 302 51 171 230p-Anisidine 246 57 130 154 962-Aminopyridine 204 58 71 872,5-Diaminotoluene (10) 273 64 220 3073-Aminopyridine 252 64 133 119p-Tolylhydrazine 244d 65 130 146m-Phenylenediamine 283 64 191 240 1940-Nitroaniline 71 94 98 1044-Amino-2-nitrotoluene 78 145 172 160m-Aminoacetanilide 88 1913,4-Diaminotoluene (11) 265 90 210 264 179Ethyl p-aminobenzoate (12) 92 110 1486-Nitro-2-aminotoluene 92 158 1683-Nitro-2-aminotoluene 97 158m-Aminoacetophenone 99 1292,4-Diaminotoluene (13) 292 99 224 224 191o-Phenylenediamine 257 102 186 301 186p-Aminoacetophenone 294 106 167 205 1282-Amino-4-nitrotoluene 107 151 186 1722-Naphthylamine C 294 113 134 162 102m-Nitroaniline 114 155 157 1364-Amino-3-nitrotoluene 117 96 148 1025-Nitro-l-naphthylamine 119 220 1831-Nitro-2-naphthylamine 126 123 168 156p-Aminoazobenzene 126 145 211Benzidine C 126 317 352 235o-Tolidine (14) C 129 314 2652-Amino-5-nitrotoluene 129 202 174 159o-Aminoacetanilide 1322,6-Dinitroaniline 138 197p- Phenylenediamine 267 141 304 >300 2472-Nitro-l-naphthylarnine 144 199 175Anthranilic acid 146 185 181 214p- Nitroaniline 148 216 199 139p- Nitrophenylhydrazine 157d 205 1934-Aminopyridine 158 150 202p-Aminoacetanilide 163 304Sulphanilamide (15) 166 219 284 211m-Aminobenzoic acid 174 2502,4-Dinitroaniline 180 121 220p-Aminobenzoic acid 187 251 278 212Picramide (16) 190 230 196 2114-Nitro-l-naphthylamine 195 190 224 1732,4-Dinitrophenylhydrazine 198d 198 2072-Aminoanthraquinone 302 257 228 271

1374


Table 10.33 Primary aromatic amines (continued)


amideQC

C-H alogeno-amines

o-Chloroaniline 209 88 99 1302-Amino-3-chlorotoluene 215 1204-Amino-3-chlorotoluene 223 7 113 137 110m-Chloroaniline 230 79 122 1212-Amino-4-chlorotoluene 237 22 1404-Amino-3-bromotoluene 240 26 117 1492-Amino- 5-chlorotoluene 241 29 140 142 1252-Amino-6-chlorotoluene 245 159 173m-Bromoaniline 251 18 88 120m-Iodoaniline 25 119 1512-Amino-4-bromotoluene 255 32 165o-Bromoaniline 229 32 99 1162,5-Dichloroaniline 255 50 132 1202-Amino-5-bromotoluene 240 59 157 115o-Iodoaniline 60 110 1392,4-Dichloroaniline 245 63 146 117 128p-Iodoaniline 63 184 222p-Bromoaniline 66 167 204 134p-Chloroaniline 232 71 179 193 1222,4,6-Trichloroaniline 263 78 206 1742,4-Dibromoaniline 79 146 1342,6-Dibromoaniline 84 2102,4-Diaminochlorobenzene 88 243 1782-Chloro-4-nitroaniline 108 139 1614-Chloro-2-nitroaniline 116 1042,4,6-Tribromoaniline 120 232 198

Amino-phenol4

2,4-Diaminophenol (17) 79d 222 (di) 231m-Aminophenol 123 101 (di) 153 (di)Picramic acid (18) 169 201 (N) 229 (N)5-Amino-2-hydroxytoluene 173 103 (di) 194o-Aminophenol 174 124 (di) 184 (di) 141p-Aminophenol 186d 150 (di) 234 (di) 1258-Amino-2-naphthol 207 165 208l-Amino-Z-naphthol dec. 206 235

t This compound is benzimidazole.t See also Table 10.34 and Table 10.35 for secondary and tertiary amines having a nuclear hydroxylsubstituent,

(I) 2,5-Dimethylaniline. (5) o-Methoxyaniline,(2) 2,6-Dimethylaniline. (6) o-Ethoxyaniline,(3) 2,4-Dimethylaniline. (7) 2,4,6-Trimethylaniline.(4) 3,5-Dimethylaniline.

1376


Toluene-p- Benzylidene Picrate 3-Nitro- 2,4-Dinitro- Formyl Phenylsulphon- derivative QC phthalimide phenyl derivative thioureaamide QC QC derivative QC QCQC QC

105 34 134 136 150 77 156

138 177 172 184 58 124

156191 (N)110139252

89182

199190

129140

146150

(8) o-Xenylamine.(9) p-Xenylamine.

(10) 2,5-Tolylenediamine.(11) 3,4-Tolylenediamine.(12) Benzocaine.(13) 2,4-Tolylenediamine.

(14) 4,4'-Diamino-3,3'-dimethylbiphenyl.(15) p-Aminobenzenesulphonamide.(16) 2,4,6-Trinitroaniline.(17) Hydrochloride = Amidol.(18) 2-Amino-4,6-dinitrophenol.

1377

,. PHYSICAL CONSTANTS OF ORGANIC COMPOUNDSTable 10.34 Secondary aromatic amines

Amine B.P. M.P. Acetamide BenzamideQC QC QC QC

N- Methylbenzylamine 181N-Methylaniline 194 103 63N-Ethylbenzylamine 199N-Ethylaniline 205 55 60N -Methyl-m-toluidine 206 66N- Methyl-o-toluidine 208 56 66N-Methyl-p-toluidine 210 83 53N-Ethyl-o-toluidine 214 72N-Ethyl-p-toluidine 217 39N-Ethyl-m-toluidine 221 72N-Propylaniline 222 47N -Butylaniline 240 56N-Methyl-1-naphthylamine 294 94Dibenzylamine 300d 112N-Methyl-2-naphthylamine 317 51 84N -Ethyl-2-naphthylamine 315 49N-Ethyl-1-naphthylamine 325 680-Nitro-N-methylaniline 37 70N -Benzylaniline 306 38 58 107Diphenylamine 302 54 103 180m-Nitro-N -ethylaniline 60 89N-Phenyl-1-naphthylamine 62 115 152m-Nitro-N -methylaniline 68 95 155Di-p-tolylamine 330 79 88 125p-Hydroxy-N-methylaniline 86 43 (mono) 174 (mono)o-Hydroxy-N-methylaniline 96 64 (di) 160 (mono)p- Nitro-N -ethylaniline 96 119N -Phenyl-2-naphthylamine 108 93 136p-Nitro-N-methylaniline 152 152 111Indole 254 52 68Carbazole 355 246 69 98

1378


Benzene- Toluene-p- Picrate Formyl Other derivatives QCsulphonamide sulphonamide QC derivativeQC QC QC

9579 95 145 Phthalamic acid, 194

50 118 Urea (with PhNCO), 8188 138 Phthalamic acid, 204

120 9060 131 N-Nitroso*, 52 C7571

54 Phthalamic acid, 22556 Phthalamic acid, 204

16468 52

78 145 N-Nitroso, 88 C

N-Nitroso, 36 C119 140 48 N-Nitroso, 58 C123 142 182 74 N-Nitroso, 67 C

83 N-Nitroso, 76 CN-Nitroso, 101 C

135 (mono) N-Nitroso, 136 CN-Nitroso, 130 CN-Nitroso, 120 C

120 N-Nitroso, 104 C187 52 N-Nitroso, 171 C

137 185

* The particularly powerful carcinogenic properties of these compounds should be noted.

1379


Table 10.35 Tertiary amines

Amine B.P. QC M.P. Methiodide(JmmHg) QC QC

Trimethylamine 3 230Triethylamine 89Triallylamine 155Tripropylamine 156 208Tributylamine 212 186Tri-isopentylamine 245Tripentylamine 257

N,N-Dimethylbenzylamine 184 179N,N-Dimethyl-o-toluidine 185 210N ,N-Dimethylaniline 193 228N-Methyl-N-ethylaniline 201 125N,N-Diethyl-o-toluidine 210 224N ,N-Dimethyl-p-tol uidine 211 220N,N-Dimethyl-m-toluidine 212 177N,N-Diethylaniline 218 102N,N-Diethyl-p-toluidine 229 184N,N-Diethyl-m-toluidine 231N,N-Di-n-propylaniline 245 156N,N-Di-n-butylaniline 271N ,N -Dimethyl-l-naphthylamine 273N -Benzyl-N-methylaniline 306 164N -Benzyl-N-ethylaniline 186/22 161N,N-Dimethyl-2-naphthylamine 305 47p-Bromo-N,N-dimethylaniline 264 55Dibenzylaniline 300 70 135p-Hydroxy-N,N-dimethylaniline 76 201p-Nitroso-N,N-dimethylaniline 87Tribenzylamine 380 92 184Triphenylamine 365 127p-Ni tro- N,N-dimethylaniline 163

Pyridine 115 118e-Picoline (1) 129 2272,6-Lutidine (2) 142 238y-Picoline 143 152{J- Picoline 144 922,4-Lutidine 159 1132,5-Lutidine 1602,3-Lutidine 1642,4,6-Trimethylpyridine (3) 1725-Ethyl-2-methylpyridine 1783-Ethyl-4-methylpyridine 196Ethyl nicotinate 223Nicotine 246Methyl nicotinate 204 382,2'-Bipyridyl 273 70

Quinoline 238 72* (133)tIsoquinoline 242 24 159Quinaldine (4) 247 1958-Methylquinoline 2486-Methylquinoline 258 219Lepidine (5) 262 1742,4-Dimethylquinoline 264 264

1380

TABLES OF DER1VATlVES 10

I. PHYSICAL COISTAITS OF ORGAIlC COIPOUIOSTable 10.35 Tertiary amines (continued)

Amine B.P. M.P. MethiodideQC QC QC

6-Methoxyquinoline 284 26 2367-Methylquinoline 252 398-Methoxyquinoline 283 50 1602,6-Dimethylquinoline 267 60 2378-Hydroxyquinoline 267 76 1438-Nitroquinoline 926-Nitroquinoline 154 2456-Hydroxyquino1ine 193

3-Chloropyridine 1493-Bromopyridine 170 1652-Chloropyridine 1702-Bromopyridine 1943,5-Dibromopyridine 222 112 2742,6-Dibromopyridine 249 119

6-Bromoquinoline 278 19 2782-Chloroquinoline 267 386-Chloroquinoline 262 41 2482-Bromoquinoline 49 210Acridine 111 224Hexamethylenetetramine 280 Sub. 190

* Monohydrate. t Anhydrous.

1382


1383


Table 10.36 Amino acids

Amino acid MP.* Benzoate 3,5-Dinitro- PhenylureidoQC QC benzoate acid

QC QC

N-Phenylglycine 126 63 195Anthranilic acid 145 182 278 181m-Aminobenzoic acid 174 248 270 270( )-3-Amino-2-methylpropanoic 177p-Aminobenzoic acid 186 278 290 3003-Aminopropanoic acid 196 165 202 174(+ )- or ( - j-Glutamic acid 198 138 217p-Aminophenylacetic acid 200 206()-Proline 203 217 170Sarcosine 210 103 153(+ )- or ( - j-Proline 222 170(+ )- or ( - j-Lysine 224 150 169 184(+ )- or ( - j-Asparagine 227 189 196 164()-Glutamic acid 227 156(+ )-Serine 228Glycine 232 187 179 163( )-Threonine 235 148( )-Arginine 238 230()-Serine 246 171 183 169(+ )- or (- )-Threonine 253 148(+ )- or ( - j-Cystine 260 181 180 160(+ )- or (- j-Aspartic acid 272 185 162()-Methionine 272 151()-Phenylalanine 274 188 93 182()-Tryptophan 275 188 240(+ )- or (- )-Histidine 277 249 1892-Amino-2-methylpropanoic Sub. 280 202d( j-Aspartic acid 280 165(+ )- or ( - j-Methionine 283 150 95(+)- or (- )-Isoleucine 284 117 120(+ )- or ( - )-Tryptophan 289 104 233 166( )-Isoleucine 292 118( )-a-Alanine 295 166 177 174(+ )- or ( - )-a-Alanine 297 151 190()-Valine 298 132 164()-Norvaline 303 182( )-2-Aminobutanoic 307 147 170(+)- or (- )-Valine 315 127 181 147()-Tyrosine 318 197 254(+ )- or ( - )-Phenylalanine 320 146 93 181( )-Norleucine 327( )-Leucine 332 141 165(+ )- or ( - j-Leucine 337 107 187 115(+ )- or ( - )-Tyrosine 344 166 104( j-Asparagine >300()-Histidine()-Lysine 249 196

These melting points are probably better described as decomposition points and their values willdepend somewhat upon the rate of heating. Many of the naturally-occurring amino acids are (-)-rotatory.

1384


1385


Table 10.37 Aromatic nitro compounds

Nitro compound B.P. M.P. Nitro compound B.P. M.P.QC QC QC QC

Nitrobenzene (I) 221 6 m-Nitrobenzyl chloride 46o-Nitrotoluene (2) 222 o-Nitrobenzyl bromide 472-Nitro-m-xylene 226 o-Nitrobenzyl chloride 49m-Nitrotoluene (3) 229 16 2,4-Dinitrocholorobenzene 315 512-Nitro-p-xylene 237 o-Nitroiodobenzene 543-Nitro-o-xylene 240 15 m-Nitrobromobenzene 256 564-Nitro-m-xylene 244 2,5-Dichloronitrobenzene 267 562-Nitro-p-cymene (4) 264 m-Nitrobenzyl bromide 590-Nitroanisole 265 10 p-Nitrobenzyl chloride 71m-Nitrophenetole 267 2 o-Nitrobenzyl iodide 75m-Nitrobenzyl alcohol 27 2,4-Dinitrobromobenzene 754-Nitro-o-xylene 254 30 Picryl chloride 83m-Nitrophenetole 284 34 p- Nitrochlorobenzene 242 832-Nitrobiphenyl 320 37 2-Nitro-p-dibromobenzene 84m-Nitroanisole 258 39 m-Nitrobenzyl iodide 86Nitromesitylene 255 44 2,4-Dinitroiodobenzene 88p-Nitrotoluene 238 54 p-Nitrobenzyl bromide lOOp-Nitroanisole 259 54 p-Nitrobromobenzene 256 127w- Nitrostyrene 260

TABLES OF DERIVATlVES 10

Table 10.38 AIiphatic nitro compounds

Nitro compound B.P. QC diV' ""no(JmmHg)

Nitromethane 101 1.137 1.381Nitroethane 114 1.050 1.3922-Nitropropane 120 0.988 1.394l-Nitropropane 131 1.001 1.4011-Nitrobutane 152 0.971 1.410l-Nitropentane 66/16 0.953 1.418l-Nitrohexane 82/15 0.940 1.423Phenylnitromethane 227 1.160 1.532

Table 10.39 Thiols

Thiol B.P. M.P. 2,4- 2,4- 3,5- HydrogenQC QC Dinitro- Dinitro- Dinitro- 3-nitro-(JmmHg) phenyl- phenyl- thio- thio-

thioether sulphone benzoate phthalateQC QC QC

Methanerhiol 6 128 190Ethanethiol 36 115 160 62 149Propane-2-thiol 58 95 141 84 145Propanethiol 67 81 128 52 1372-Methylpropanethiol 88 76 106 64 136Prop-2-ene-1-thiol 90 72 105Butanethiol 97 66 92 49 1443-Methylbutanethiol 117 59 95 43 145Pentanethiol 126 80 83 40 132Hexanethiol 151 74 97Cyclohexanethiol 159 148 172Heptanethio1 176 82 101 53 132Octanethiol 199 78 98Nonanethiol 220 86 92Decanethiol 114/13 85 93Dodecanethiol 154/24 89 101Hexadecanethiol 51 91 105

1,2-Ethane dithiol 146 2481,3-Propane dithiol 173 1941,4-Butane dithiol 1961,5-Pentane dithiol 217 1701,6-Hexane dithiol 237 218

Thiophenol 169 121 161 149 130Phenylmethanethiol 194 130 183 120 1370-Thiocresol 194 15 101 155m-Thiocresol 195 91 145p-Thiocresol 195 44 103 1901-Phenylethanethiol 199 90 1332-Phenylethanethiol 105/231-Thionaphthol 161/20 1762-Thionaphthol 162/20 81 1454-Mercaptobiphenyl 111 146 1702eFurylmethanethiol 84/65 1302-Thienylmethanethiol 166 119 143

1387

10 PHYSICAL CONSTAITS OF ORGANIC COMPOUIoS

Table 10.40 Sulphonic acids

Note. Aromatic sulphonic acids are usually hygroscopic solids and do not generally have sharpmelting points: they are frequently supplied in the form of their sodium (or other metal) salts. It istherefore not possible to classify them in order of increasing melting points. In this table

1388

Acid

BenzenesulphonicToluene-o-sulphonicToluene-m-sulphonicToluene-p-sulphonico-Chlorobenzenesulphonicm-Chlorobenzenesulphonicp-Chlorobenzenesulpohonico-Bromobenzenesulphonicm-Bromobenzenesulphonicp- Bromobenzenesulphonic0-Nitrobenzenesulphonicm-Nitrobenzenesulphonicp- NitrobenzenesulphonicSulphanilicOrthanilicMetanilico-Sulphobenzoic (salt)m-Sulphobenzoicp-SulphobenzoicPhenol-p-sulphonicThymolsulphonico-Xylene-t-sulphonicm-Xylene-4-sulphonicp-XylenesulphonicNaphthalene-l-sulphonicNaphthalene-2-sulphonicAnthraquinone-l-sulphonicAnthraquinone-2-sulphonic1-Naphthylamine-4-sulphonicI-Naphthylamine-5-sulphonicl-Naphthylamine-e-sulphonicI-Naphthylamine-7-sulphonic1-Naphthylamine-8-sulphonic2-Naphthylamine-l-sulphonic2-Naphthylamine-6-sulphonicl-Naphthol-z-sulphonicI-Naphthol-4-sulphonic1-Naphthol-5-sulphonic2-Naphthol-l-sulphonic2-Naphthol-6-sulphonic2-Naphthol-8-sulphonicBenzene-o-disulphonicBenzene-m-disulphonicBenzene-p-disulphonicNaphthalene-I,4-disulphonicNa phthalene-I ,5-disulphonicNaphthalene-l.e-disulphonicNaphthalene-2,6-disulphonicNaphthalene-2,7-disulphonic2-Naphthylamine-4,8-disulphonic

SulphonamideArSO,NH,QC

153156108137188148144186154166193168179164153142

170236177

144138148150217

261206260219181

238

254229288273310298305243

S-Benzylisothio-uronium saltQC

150170

182

175

170

146

187132148206163213169213208146184137191191211195180191

300139184170104

136217218206214

257235256211210

TABLES OF OERIVATlVES 10


Table 10.40 Sulphonic acids (continued)

Acid Sulphonamide S-Benzylisothio-ArSO,NH, uronium saltQC QC

2-Naphthylamine-5,8-disulphonic 2762-Naphthylamine-6,7-disulphonic1-Na phthylamine-3,6-disulphonic1-Naphthylamine-3,8-disulphonic1-Naphthol-3,6-disulphonic 2171-Naphthol-4,8-disulphonic 2052-Na phthol-3,6-disulphonic 2332-Naphthol-6,8-disulphonic 228(+ j-Camphorsulphonic 132 210

Aliphatic sulphonic acids

Sulphonic acid B.P. Sulphonyl Sulphonamide, S-Benzyl- Sulphon-QC chloride, M.P. isothio- anilide

B.P. QC uronium salt M.P.QC M.P. QC

QC

Methane 167/10 163 90 99Ethane 177 59 115 58Propane-z- 79/18 60 84Propane-l- 78/13 52Butane-l- 75/10 45

Table 10.40A Sulphonic acids (continued)

(Arranged in the order of increasing melting points of the S-benzylisothiouronium salts.)

Sulphonic acid M.P. Sulphonic acid M.P.QC QC

1-Naphthol-4- 104 p- Bromobenzene- 170Ethane- 115 1-Naphthol-2- 170Orthanilic acid 132 o-Toluene- 1702-Naphthol-1- 136 p-Chlorobenzene- 175Naphthalene-1- 137 1-Naphthylamine-5- 1802-Naphthylamine-I- 139 p-Toluene- 182m-Nitrobenzene- 146 2-Naphthylamine-6- 184m-Xylene-4- 146 p-Xylene- 184Metanilic acid 148 Sulphanilic acid 187Benzene- 150 Naphthalene-2- 191m-Sulphobenzoic acid 163 Anthraquinone-1- 191Phenol-p- 169 l-Naphthylarnine-e- 191

1390

SulphonanilideArSO,NHPhC

2D2195

Sulphonic acid

p-ToluidinesaltQC

M.P.QC

SulphonylChlorideArSO,CIQC

16288

Sulphonic acid


SulphonacetamideArSO,NHCOCH3QC

M.P.QC

l-Naphthylamine-d-I-Naphthol-4,8-di-Benzene-o-di-o-Sulphobenzoic acido-Xylene-4-(+ j-Camphor-2-Naphthylamine-4,8-di-Naphthalene-2,7-di-Anthraquinone-Z-p-Sulphobenzoic acidThymol-Benzene-m-di-

195205206206208210210211211213213214

2-Naphthol-6-1-Naphthol-3,6-di-2-Naphthol-8-2-Naphthol-6,8-di-2-Naphthol-3,6-di-Naphthalene-Lo-di-Naphthalene-2,6-di-Naphthalene-Lo-di-2-Naphthylamine-5,8-di-I-Naphthylamine-8-

217217218228233235256257276300

1391


Table 10.41 Sulphonamides, R 'S02NH2

Sulphonamide M.P. N-Xanthyl- Sulphonamide M.P. N-Xanthyl-QC sulphon- QC sulphon-

amide amide

Butane-l- 45 2-Naphthalene- 217Propane-I- 52 o-SulphobenzimideEthane- 59 (saccharin) 226d 198Propane-2- 60 1,3-Benzenedi- 229 170m-Ethylbenzene- 86 2,7-Naphthalenedi- 242Methane- 90 1,2-Benzenedi- 2542,6-Dimethylbenzene- 96 2-Anthraquinone- 261o-Ethylbenzene- lOO 1,4-Naphthalenedi- 273Phenylmethane- 105 p-SulphonamidobenzoicToluene-m- 108 acid 280p-Ethylbenzene- 109 196 1,4-Benzenedi- 288p- Methoxybenzene- 111 1,6-Naphthalenedi- 2983,5-Dimethylbenzene- 135 1,5-Naphthalenedi- 310(+ )-Camphor-8- 137 1,3,5-Benzenetri- 3122,4-Dimethylbenzene- 137 188 1,8-Anthraquinonedi- 340Toluene-p- 137 1972,4,6-Trimethylbenzene- 142 203 Haloqeno-sulphonamidesm-Aminobenzene- 1423,4-Dimethylbenzene 144 p-Fluorobenzene- 1252,5-Dimethylbenzene- 147 176 3,4-Dichlorobenzene- 135p- Ethoxybenzene- 150 p-Chlorobenzene- 144Naphthalene-l- 150 m-Chlorobenzene- 148Benzene- 153 200 m-Bromobenzene- 154o-Aminobenzene- 153 p-Bromobenzene- 166Toluene-o- 156 183 3,4-Dibromobenzene- 175m-Ni trophenylmethane- 159 2,4-Dichlorobenzene- 180p-Aminobenzene- 2,5-Dichlorobenzene- 181

(sulphanilamide) 165 208 o-Bromobenzene 1862,3-Dimethylbenzene- 167 p- Bromophenylmethane- 188m-Nitrobenzene 168 o-Chlorobenzene- 188p-Nitrobenzene- 179 2,4-Dibromobenzene- 1902,4,5-Trimethylbenzene- 181 2,5-Dibromobenzene- 194o-Nitrobenzene- 193 p-Iodophenylmethane- 206p- Nitrophenylmethane- 204 2,4,6-Trichlorobenzene- 212d1-Nitro-Z-naphthalene- 214 2,3,4-Trichlorobenzene- 230d

1392

Table 10.42 Imides

Compound

N-2-BromoethylphthalimideN-PhenylmaleimideMaleimideAllyl-( l-methylbutyl) barbituric acidSuccinimideEthylhexylbarbituric acid (Ortal)Ethylbutylbarbituric acid (Neonal)N -2-HydroxyethylphthalimideEthyl-(l-methylbutyl)barbituric acid (Pentobarbital)Allylisopropylbarbituric acid (Alurate)Ethylisopentylbarbituric acid (Amytal)N-PhenylsuccinimideAlloxan (4H 20 )Ethylphenylbarbituric acid (Phenobarbital)Diallylbarbituric acid (Dial)Diethylbarbituric acid (Veronal)Ethylisopropylbarbituric acid (l pral)N-Phenylphthalimide3-Nitrophthalimideo-Sulphobenzimide (saccharin)PhthalimideBarbituric acidNaphthalimide

M.P. QC

829193

100125126128128130137155156170d172173190201205216226d233245d300


Table 10.43 Nitroso, azo, azoxy and hydrazo compounds*

Compound

N itroso compounds

MethylphenylnitrosoamineEthylphenylnitrosoaminep- Nitrosotoluenem-NitrosotolueneN -NitrosodiphenylamineNitrosobenzeneo-Nitrosotoluenep-Nitroso-N-ethylanilinep- Nitroso-NN -diethylanilinep-Nitroso-NN:dimethylanilinel-Nitrosonaphthalenel-Nitroso-z-naphtholp- Nitroso-N -methylanilinep-Nitrosophenolp-Nitrosodiphenylamine2-Nitroso-l-naphthol4-Nitroso-l-naphthol

Azo compounds

2,2'-Dimethylazobenzene3,3'-DimethylazobenzeneAzobenzene4-Anilinoazobenzene3,3'-Diethoxyazobenzene

B.P. 120QCj13 mmHgB.P.134

QCj16mmHg

MP. QC

485366687278848798

109118125d144152d198

5555688291

1393


Table 10.43 Nitroso, azo, azoxy and hydrazo compounds*(continued)

Compound

Azo compounds (continued)

3,3'-Dichloroazobenzenep-Dimethylaminoazobenzene Cp-Aminoazobenzene4-Hydroxy-3-methylazobenzene2,2'-Diethoxyazobenzenel-Phenylazo-z-naphthol2,2'-Dichloroazobenzene2-Phenylazo-l-naphthol4,4'- Dimethylazobenzeneo-Azobiphenylp-Hydroxyazobenzene4,4-Diethoxyazobenzene4,4'-Dichloroazobenzene1,1'-Azonaphthalene4-Phenylazo-l-naphthol2,2'-Azonaphthalenep-Azobiphenyl

Azoxy compounds

Azoxybenzene3,3'-Dimethylazoxybenzene3,3'-Diethoxyazoxybenzene3,3'-Dimethoxyazoxybenzene2,2'-Dichloroazoxybenzene2,2'-Dimethylazoxybenzene4,4'-Dimethylazoxybenzene2,2'-Dimethoxyazoxybenzene3,3'-Dichloroazoxybenzene2,2'-Diethoxyazoxybenzene4,4'-Dimethoxyazoxybenzene1,1'-Azoxynaphthalene4,4'-Diethoxyazoxybenzene4,4'-Dichloroazoxybenzeneo-Azoxybiphenyl2,2'-Azoxynaphthalenep-Azoxybiphenyl

Hydrazo compounds

3,3'-Dimethylhydrazobenzene4,4'- Diethoxyhydrazobenzene2,2'-Diethoxyhydrazobenzene2,2'-Dimethoxyhydrazobenzene3,3'-DiethoxyhydrazobenzeneHydrazobenzene4,4'-Dimethylhydrazobenzene2,2'-Hydrazonaphthalene2,2'-Hydrazodiphenol1,1'-Hydrazonaphthalene2,2'-Dimethylhydrazobenzene4,4'-Hydrazodibiphenyl2,2'-Hydrazodibiphenyl

M.P. QC

101117126128131134137138144145152160188190206d208250

363950525660708197

102119127138158158168212

388689

102119127134141148153165169182

* All these compounds should be regarded as potential carcinogens; thosemarked C are subject to legal control.

TABLES OF DERIVATIVES ,.Table 10.44 Miscellaneous sulphur compounds

Compound B.P. QC M.P. QC tPfl nlr(JmmHg)

Dimethyl sulphide 38 0.849 1.436Ethyl methyl sulphide 66 0.846 1.440Diethyl sulphide 92 0.837 1.442Di-isopropyl sulphide 119 0.817 1.440Di-allyl sulphide 140Dipropyl sulphide 142 0.839 1.449Di-isobutyl sulphide 169 0.826 1.447Di-s-butyl sulphide 165 0.835 1.451Dibutyl sulphide 187 0.840 1.453Di-isopentyl sulphide 86/5 0.834 1.453Dipentyl sulphide 85/4 0.841 1.456Dihexyl sulphide 114/4 0.841 1.459Diheptyl sulphide 142/4 0.842 1.461Dioctyl sulphide 162/4 0.845 1.469Diphenyl sulphide 145/8 1.114 1.633Dibenzyl sulphide 50Di-p-tolyl sulphide 57

Dimethyl disulphide 109 1.065 1.526Diethyl disulphide 153 0.992 1.507Di-isopropyl disulphide 176 0.944 1.492Dipropyl disulphide 194 0.960 1.498Di-allyl disulphide 100/48Di-isobutyl disulphide 215 0.928 1.487Di-t-butyl disulphide 65/5 0.923 1.490Dibutyl disulphide 231 0.938 1.493Dipentyl disulphide 119/7 0.922 1.489Di-isopentyl disulphide 115/9 0.919 1.496Di-p-tolyl disulphide 48Diphenyl disulphide 60Dibenzyl disulphide 73

Dimethyl sulphoxide 189 18.5 1.101 1.477Diethyl sulphoxide 88.9/5 14(4-6)Dipropyl sulphoxide 82/15 22-3 0.965 1.466Di-isopropyl sulphoxide 68.5Dibutyl sulphoxide 32 0.832 1.467Diphenyl sulphoxide 70Di-p-tolyl sulphoxide 95Dibenzyl sulphoxide 134

Dipropyl sulphone 29Dibutyl sulphone 44Diethyl sulphone 248 74Trional 76Dimethyl sulphone 238 109Sulphonal 126Diphenyl sulphone 128Dibenzyl sulphone 150Di-p-tolyl sulphone 159

Methyl thiocyanate 131 1.082Ethyl thiocyanate 147 1.024 1.465Isopropyl thiocyanate 151Propyl thiocyanate 165 0.981 1.463Butyl thiocyanate 184 0.961 1.464

1395

10 PHYSICAL CONSUNTS OF ORGANIC COMPOUNDS

Table 10.44 Miscellaneous sulphur compounds (continued)

Compound B.P. QC M.P. QC d'#"(JmmHg)

Benzyl thiocyanate 38Allyl isothiocyanate 152 1.0WPhenyl isothiocyanate 221 1.134

Thiophene 84 1.062

Methyl benzenesulphonate 150/15 1.273Ethyl benzenesulphonate 156/16 1.219Propyl benzenesulphonate 162-3/15 1.180Methyl toluene-p-sulphonate 28Ethyl toluene-p-sulphonate 173/15 33Propyl toluene-p-sulphonate 165/10Butyl toluene-p-sulphonate 175/10Phenyl toluene-p-sulphonate 96

N-Allylthiourea 78N,N'-Di-m-tolylthiourea 112N-Phenylthiourea 154N,N'-Diphenylthiourea

(thiocarbanilide) 154N,N'-Di-o-tolylthiourea 166N,N'-Di-p-tolylthiourea 178Thiourea C 180Thiosemicarbazide 182

1396

nil'"

1.5241.651

1.525


Table 10.45 Miscellaneous phosphorus compounds

Phosphate B.P. QC M.P. QC tlfJ nlf"(fmmHg)

Trimethyl 62/5 (197) 1.214 1.396Triethyl 76/5 (216) 1.070 1.405Tri-isopropyl 84/5 0.987 1.406Tripropyl 108/5 1.012 1.416Tri-isobutyl 117/5 0.968 1.419Tributyl 139/6 0.977 1.425Tri-isopentyl 143/3Tripentyl 167/5 0.961 1.432Tri-o-cresyl 264/20Tri-m-cresyl 274/17 26Triphenyl 245/11 50Tribenzyl 65Tri-p-cresyl 78Tri-2-naphthyl 111

Phosphite B.P. QC M.P. QC ~9' ""no(/mmHg)

Trimethyl 112 1.052 1.410Triethyl 157 0.969 1.414Tri-isopropyl 60/9 0.918 1.412Tripropyl 207 0.952 1.427Tri-isobutyl 235 0.917 1.425Tributyl 120/10 0.923 1.432Tripentyl 123/6 0.901 1.433Triphenyl 228/12 24Tri-o-cresyl 238/11Tri-m-cresyl 235/7Tri-p-cresyl 238/7Dimethyl hydrogen 72/25 1.200 1.404Diethyl hydrogen 66/6 1.079 1.408Di-isopropyl hydrogen 90/25 0.996 1.407Dipropyl hydrogen 92/11 1.019 1.416Di-isobutyl hydrogen 106/12 0.976 1.420Dibutyl hydrogen 119/7 0.995 1.423

1397


Table 10.46 Esters of inorganic acids

Ester B.P. QC tP.g' ""no(JmmHg)

Nitrites

Methyl nitrite -12Ethyl nitrite 17 0.907 1.331

(10 QC) (10 QC)Propyl nitrite 48 0.886 1.360Isopropyl nitrite 45 0.856Butyl nitrite 76 0.882 1.377Isobutyl nitrite 67 0.871 1.373s-Butyl nitrite 68 0.872 1.371t-Butyl nitrite 63 0.867 1.369Pentyl nitrite 104 0.882 1.389Isopentyl nitrite 99 0.871 1.387t-Pentyl nitrite 93 0.896 1.387

Nitrates

Methyl nitrate 65 1.208 1.375Ethyl nitrate 88 1.108 1.385Propyl nitrate III 1.054 1.397Isopropyl nitrate 102 1.035 1.391Butyl nitrate 136 1.023 1.407Isobutyl nitrate 124 1.015 1.403s-Butyl nitrate 124 1.026 1.402Pentyl nitrate 157 0.996Isopentyl nitrate 148 0.998 1.413

Sulphites

Dimethyl sulphite 126 1.213 1.409Diethyl sulphite 157 1.083 1.414Dipropyl sulphite 191 1.028 1.424Di-isopropyl sulphite 170 1.006 1.415Dibutyl sulphite 91/5 0.996 1.431Di-isobutyl sulphite 210 0.986 1.427Dipentyl sulphite 111/5 0.978 1.436Di-isopentyl sulphite 98/4 0.973 1.436

Sulphates

Dimethyl sulphate C 188 1.328 1.387Diethyl sulphate 208 1.177 1.400Dipropyl sulphate 94/5 1.110 1.414Dibutyl sulphate 116/6 1.062 1.421Di-isobutyl sulphate 133/19 1.045 1.415Dipentyl sulphate 117/4 1.029 1.429

See Table 10.45 for alkyl phosphates and alkyl phosphites,

1398

APPENDICES

APPENDIX 1THE LITERATURE OF ORGANIC CHEMISTRY

At1 INTRODUCTION

The annual volume of published chemical papers has increased roughly five-foldover the past forty years. This volume of information imposes two sorts of taskson the organic chemist. Firstly, to keep abreast of developments in aspects of thesubject which are of particular interest by sampling the flow of published in-formation as it appears, and secondly, to retrieve information of interest fromthe accumulation of published material. The information which is to beretrieved may be the physical properties of a specific compound or a reliablemethod for its preparation, a comprehensive list of preparative methods, a sur-vey of recent work on a particular group of compounds, etc. Although somechemists, particularly those in large pharmaceutical companies, may have accessto the services of information scientists, many still need to maintain currentawareness and to carry out literature searches themselves, and all organicchemists need to be familiar with the nature of the chemical literature. Compu-terised methods for storage and retrieval of information are becoming increas-ingly common and accessible to the individual chemist and this trend is likely tocontinue. Given access to a good chemical library with a range of on-line facil-ities the experienced chemist should be able to obtain the information requiredwithout too much difficulty. The principal sources of such information aredescribed in this appendix. The coverage is necessarily selective and readers whorequire a more detailed treatment are recommended to consult one of thespecialised monographs on the subject.' 5

A.1.2 PRIMARY SOURCES - JOURNALS

Scientific journals are the principal method for communicating scientific in-formation. The majority of papers abstracted by Chemical Abstracts is inEnglish. These original papers are complemented by a range of other less-usedprimary literature such as patents, dissertations and theses, and reports of vari-ous kinds. Although a great number of journals are published which contain in-formation of interest to the chemist, only a small proportion of them regularlycontain material which is directly and immediately useful to the organic chemist.The most important journals dealing with organic chemistry are listed below.The standard abbreviation listed in the Chemical Abstracts Service Source Index(CASSI) is given in parenthesis.

1401

PRACTICAL ORGANIC CHEMISTRY

Acta Chemica Scandinavica. Series B. Organic Chemistry and Biochemistry(Acta Chem. Scand. Ser. B).

Angewandte Chemie. International Edition in English (Angew. Chem., Int. Ed. inEngl.).

Australian Journal of Chemistry (Aust. J. Chem.).Bulletin of the Academy of Sciences of the USSR, Division of Chemical Sciences

(English Translation). (lzvestia Akademii Nauk SSSR, Ser. Khim.) (Bull.Acad. Sci. USSR. Div. Chim. Sci. (Engl. Transl.)).

Bulletin of the Chemical Society of Japan (Bull. Chem. Soc. Japan).Bulletin de la Societe Chimique de France (Bull. Soc. Chim. Fr.).Canadian Journal of Chemistry (Can. J. Chem.).Chemical Communications (1. Chem. Soc., Chem. Commun.).Chemische Berichte (Chem. Ber.).Helvetica Chimica Acta (He Iv. Chim. Acta)Journal of the American Chemical Society (J. Am. Chem. Soc.).Journal of Chemical Research, Synopses and microfiche or miniprint (J. Chem.

Res. (S) and (M)).Journal of the Chemical Society, Perkin Transactions I, Organic and Bio-

organic Chemistry, and Perkin Transactions 2, Physical Organic Chemistry(J. Chem. Soc., Perkin Trans 1 and 2).

Journal of General Chemistry of the USSR (English Translation) (ZhurnalObschei Khimii) (1. Gen. Chem. USSR. (Engl. Transl.)).

Journal of Heterocyclic Chemistry (1. Heterocycl. Chem.).Journal of Organic Chemistry (1. Org. Chem.).Journal of Organic Chemistry of the USSR (English Translation) (Zhurnal

Organischeskoi Khimii) (1. Org. Chem. USSR (Engl. Transl.)).Journal of Organometallic Chemistry (J. Organomet. Chem.).Organic Preparations and Procedures International (Org. Prep. Proced. Int.).Synthesis (Synthesis).Synthetic Communications (Synth. Commun.).Tetrahedron (Tetrahedron).Tetrahedron Letters (Tetrahedron Lett.).

A.1.3 SECONDARY SOURCES - ABSTRACTS

Abstracting journals are publications giving contemporaneous, concise sum-maries of the various original journals and other contributions to knowledge.Each abstract usually supplies the title of the original paper, names of authors,original reference (i.e. name of journal, year of publication, volume or seriesnumber, page) and generally a brief summary of the paper. The value of theabstract in the first instance will depend on how detailed the summary is. It mustbe emphasised, however, that the reader should never be satisfied with theaccount to be found in the abstract. Ifat all possible the original work should beconsulted. The only abstracting journal in English covering all fields ofchemistry and chemical technology is Chemical Abstracts published by theAmerican Chemical Society. All organic chemists should be familiar with the useof Chemical Abstracts. Other abstracting journals such as Biological Abstractsmay contain information of interest to the organic chemist.

Chemical Abstracts was first published in 1907 and has continued ever since.

1402

APPENDIX 1

About 14000 journals are monitored but only about 300 are abstracted com-pletely. Chemical Abstracts Service Source Index (CASSI) provides a compre-hensive list of journals currently abstracted by Chemical Abstracts. Twovolumes of Chemical Abstracts are published each year, in 1988volumes 108and109, and every five years a Collective Index is published covering the tenvolumes published during the period. The publication of the Eleventh CollectiveIndex, covering Volumes 96-105 (1982-86), was completed in 1988. The docu-ments abstracted by Chemical Abstracts include journal articles, patents,reviews, technical reports, monographs, conference proceedings, symposia, dis-sertations and books. The abstracts are divided into eighty sections. The readershould consult Subject Coverage and Arrangement of Abstracts by Sections inChemical Abstracts - 1982 published by Chemical Abstracts Services for a de-scription of the subject coverage of each of the eighty sections. ChemicalAbstracts appears weekly, each week containing alternately Sections 1-34(Biochemistry and Organic Chemistry sections) and Sections 35-80 (Macro-molecular Chemistry; Applied Chemistry and Chemical Engineering; andPhysical, Inorganic and Analytical Chemistry sections). Each weekly issue ofChemical Abstracts contains two parts, the abstracts and the issue index (key-word, patent and author index). An Illustrative Key is included at the start ofeach new volume (which covers a six-month period) to assist the reader in themost effective use of the abstracts, and readers are recommended to consult thiskey for more detailed information than can be included in the present summary.Abstracts are numbered consecutively throughout each volume. Since 1976(Volume 84), each abstract is immediately preceded by the volume number inlightface type, and followed by a computer-generated check-letter by which eachreference is computer validated. Check letters have been in use since 1966(Volume 66) and should not be confused with the column fractional designa-tions (a-g) previously used to indicate the position of the abstract on the page.

The indexes of Chemical Abstracts are a key to the world's chemical andchemical engineering literature. There are six different indexes and care andpractice are required to make effective use of them. In the Chemical SubstanceIndex specified substances are identified and ordered by name; the General Sub-ject Index lists classes of substances and general subjects; the Formula Index listsspecific substances according to their molecular formula; in the Index of RingSystems cyclic skeletons and stereo parents are identified and ordered by ringanalysis; the Patent Index, which replaces the Numerical Patent Index andPatent Concordance, contains information on patent documents; and the AuthorIndex links the names of authors to the corresponding abstract. Explanatoryand illustrative matter relating to indexing is published separately as the IndexGuide. Each Collective Index has its own Index Guide. The initial Index Guidefor the Twelfth Collective Index (1987-91) was published in 1987 and will berevised and reissued three times during the five-year period. The Index Guidesprovide complete instructions on the use of Chemical Abstracts and also a com-prehensive account of the policies for selecting the names of chemical substancesin Chemical Abstracts. Appendix 11 of the Index Guide describes the organisationand use of the indexes and the relationship between them. In addition, ChemicalAbstracts Service produces a workbook which provides further instruction onthe use of Chemical Abstracts. The Ring Systems Handbook (1984) is a tool forsearching Chemical Abstracts for specific ring systems, it provides a file of dia-grams of ring systems (59510 in the 1984 edition) together with indexes of

1403

PRACTICAL ORGANIC CHEMISTRY

molecular fo

practical organic chemistry 5ed - vogel

Documents

butyl ethyl

ethyl hexyl

cyclopentyl ethyl

cyclohexyl ethyl

ethyl vinyl

allyl ethyl

butyl methyl

cyclopentyl methyl