The alkaloids fall into two chemical groups: (i) derivatives of isoquinoline, including papaverine, narcotine, gnoscopine (racemic narcotine), narceine, laudanosine, laudanine, cotarnine, hydrocotarnine (the last two do not occur in opium), and (2) derivatives of phenanthrene, including morphine, codeine, thebaine.
Phenazone is an isomer of phenazine, to which it bears the same relation that phenanthrene bears to anthracene.
By fusing two nuclei we obtain the formula of naphthalene, C 1 oH 8; by fusing three, the hydrocarbons anthracene and phenanthrene, C14H10; by fusing four, chrysene, C18H12, and possibly pyrene, C16H1n; by fusing five, picene, C22 H 14.
Methane, tetrachlormethane, &c., to yield aromatic compounds when subjected to a high temperature, the so-called pyrogenetic reactions (from Greek 7rup, fire, and - yon, fco, I produce); the predominance of benzenoid, and related compounds-naphthalene, anthracene, phenanthrene, &c.-in coal-tar is probably to be associated with similar pyrocondensations.
Thomsen then investigated heats of combustion of various benzenoid hydrocarbons - benzene, naphthalene, anthracene, phenanthrene, &c. - in the crystallized state.
The next members are the -isomers anthracene and phenanthrene, C14H,0, formed from three benzene nuclei.
Here we shall only discuss the structure of these compounds in the light of the modern benzene theories; reference should be made to the articles Naphthalene, Anthracene and Phenanthrene for syntheses, decompositions, &c.
Benzenoid rings as represented by the symbols: - Anthracene Phenanthrene In both cases the medial ring is most readily attacked; and various formulae have been devised which are claimed by their authors to represent this and other facts.
(7) (2) Phenanthrene is regarded by Armstrong as represented by (3), the lateral rings being benzenoid, and the medial ring fatty; Bamberger, however, regards it as (4), the molecule being (3) (4) entirely aromatic. An interesting observation by Baeyer, viz.
PHENANTHRENE, C14H10, a hydrocarbon isomeric with anthracene, with which it occurs in the fraction of the coal tar distillate boiling between 270°-400° C. It may be separated from the anthracene oil by repeated fractional distillation, followed by fractional crystallization from alcohol (anthracene being the less soluble), and finally purified by oxidizing any residual anthracene with potassium bichromate and sulphuric acid (R.
With picric acid it forms a sparingly soluble picrate, which melts at 145 0 C. On the condition of phenanthrene in alcoholic solution see R.
Phenanthrene-quinone, [C 6 H 4] 2 [CO] 21 crystallizes in orange needles which melt at 198° C. It possesses the characteristic properties of a diketone, forming crystalline derivatives with sodium bisulphite and a dioxime with hydroxylamine.
On the constitution of phenanthrene see CHEMISTRY: § Organic.
RETENE (methyl isopropyl phenanthrene), CisHis, a hydrocarbon present in the coal-tar fraction, boiling above 360° C.; it also occurs in the tars obtained by the distillation of resinous woods.
For naphthalene quinones see Naphthalene; for anthracene quinone see Anthraquinone; and for phenanthrene quinone see Phena Nt H Rene.
FLUORANTHENE, C15H10, also known as idryl, a hydrocarbon occurring with phenanthrene, pyrene, diphenyl, and other substances in "Stupp" fat (the fat obtained in working up the mercury ores in Idria), and also in the higher boiling fractions of the coal tar distillate.
The hydrocarbons are separated from the "Stupp" by means of alcohol, the soluble portion on distillation giving first phenanthrene and then a mixture of pyrene and fluoranthene.
The presence of the phenanthrene nucleus and the chain system CH 3 N C C follows from the fact that these alkaloids, by appropriate treatment, yield a substituted phenanthrene and also dimethylaminoethanol (CH3)2N CH2 CH20H.
Formulae have been proposed by Pschorr and Knorr explaining this and other decompositions (in Pschorr's formula the morphine ring system is a fusion of a phenanthrene and pyridine nucleus); another formula, containing a fusion of a phenanthrene with a pyrrol ring, was proposed by Bucherer in'1907.
Distilled with zinc dust morphine yields phenanthrene, pyridine and quinoline; dehydration gives, under certain conditions, apomorphine, C17H17N02, a white amorphous substance, readily soluble in alcohol, either and chloroform.
One of the most important derivatives of diphenyl, from the theoretical point of view, is diphenic acid or diorthodiphenyl carboxylic acid, which can be obtained from diparadiaminodiphenyldiorthocarboxylic acid, H2N < j - < I > NH 2, or from phenanthrene, the consti Hooc Cooh tution of which it determines.