Mayer, Fritz; English, Frank Albert published the artcile< Pschorr's phenanthrene synthesis. II>, Name: (9Z,12Z)-Methyl octadeca-9,12-dienoate, the main research area is .
The preparation of ethylphenanthrenes is desirable in order to clear the constitution of the α- and β-ethylphenanthrenes of Pschorr (Ber. 39, 3124(1918). This would perhaps enable one to decide between the two morphine formulas of Knorr and Freund. I. Condensation experiments with o-ethylphenylacetic acid and o-ethvibenzaldehyde. I-Ethyl-z-hydroxymethylbenzene (ethylbenzyl alcohol), EtC6H4CH2OH, is obtained by the electrolytic reduction of a dilute H2SO4 solution of EtC6H4CO2H, using a Pb electrode, 28 amp. and a temperature of 50-60°. After 6 hrs. the operation is interrupted, the product diluted with H2O, shaken with Et2O, the acid removed by NH4OH and the alc. distilled It is a colorless liquid with a slight aromatic odor, b. 229°. 68.5 g. alc. and 120 cc. cold saturated HBr, shaken 1.5 hrs., gave the bromide EtC6H4CH2Br, slightly bluish green liquid, b. 225°, m. 34°. It attacks the mucous membranes. The nitrile EtC6H4CH2CN is obtained in 86% yield by heating 18.8 g. NaCN in 280 cc. 80% alc. with 50 g. of bromide in 50 g. 96% alc. for 1 hr., oil with the odor of HCN, b. 257-8°. Upon saponification this yields the acid EtC6H4CH2CO2H, m. 83.5°. Ethyl ester, colorless, odorless oil. The aldehyde cannot be prepared from the acid by Mettler’s method (C. A. 3,540). Piria’s method (Ber. 13, 1413(1880) gave a 25% yield (distillation of the Ca salts of the acids). Oxidation with K2Cr2O7 gave a 67% yield, while Sommelet’s method (D. R. P. 268,786, heating the urotropine addition product of the bromide in absolute alc. for 2 hrs.) gave 33.6%. o-Ethylbenzaldehyde is an odorless oil, b753 210°. Further experiments were also made with Sommelet’s reaction. o-O2NC6H4CH2Cl and urotropine form an addition product by boiling with CHCl3 for 45 min., turns brown at 180°, m. 184° (decomposition). Heated 1 hr. with 60% alc., it forms tri-[o-nitrobenzyl]trimethylenetriamine, yellowish white crystals, m. 112°. When heated 9 hrs. with concentrated HCl, HCHO is given off and o-nitrobenzylamine is formed, of which the hydrochloride and the picrate were analyzed. In the same way, p-O2NC6H4CH2Cl and urotropine form an addition product, decompose 186°, which yields tri-[p-nitrobenzyl]trimethylenetriamine, m. 161°. 2-ClC6H4CH2Cl and urotropine form an addition product which decomposes 203°, and which yields o-ClC6H4CHO, b. 213-4°. o-EtC6H4CHO (4.5 g.), o-O2NC6H4CH2CO2Na (6.5 g.), Ac2O and ZnCl2 were heated for 10 hrs. at 120°. Only about 1/3 g. of material was obtained, which, crystallized from H2O, forms light yellow crystals, m. 183.5°. The product C9H9O3N is soluble in alkali, does not react with NH4OH and FeSO4 or with H2SO4. α-o-Ethylphenyl-β-o-nitrophenylacrylic acid, C17H15O4N, is formed from 5.1 g. of EtC6H4CH2CO2K and 3.8 g. of o-O2NC6H4CHO by heating at 100° with 0.5 g. ZnCl2 and 20 cc. Ac2O for 48 hrs. Crystallized from C6H6 it m. 194°. Reduced with FeSO4 and NH4OH, it forms α-o-ethylphenyl-β- o-aminophenylacrylic acid, crystals, m. 178-9°. Upon diazotizing and pouring into H2O, the HO acid results, instead of 8-ethylphenanthrenecarboxylic acid. II. Condensation experiments with m-ethylphenylacetic acid. 3-EtC6H4NH2 was prepared by heating 1.35 g. m-H2NC6H4COMe with 60 g. N2H44.H2O for 8 hrs. at 160° and then heating 100 g. of the resulting mixture with 120 g. N2H4-H2O 15 hrs. at 210°. The yield is about 50%. When diazotized, treated with CuCN and the nitrile saponified, I-ethylbenzene-3-carboxylic acid results, m. 40-44°. I-Hydroxymethyl-3-ethylbenzene (ethylbenzyl alcohol), EtC6H4CH2OH, is obtained by reducing the acid in alc. H2SO4 with 35 amp. at 55° for 6 hrs.; it is a slightly aromatic oil, b758 at 227°. The bromide is formed by the action of cold saturated HBr and is changed into the cyanide by the action of KCN, b761 250-4°. Saponified with 80% KOH in the presence of 30% H2O2, 3-ethylphenylacetic acid results in 97% yield, white scales, m. 62-4°. When 5.4 g. of the alc. are oxidized with 4 g. K2Cr2O7 in 6o cc. 10% H2SO4, and the reaction product is shaken with Et2O, 67% of the aldehyde results, b762 200-14°. α-m-Ethylphenyl-β-o-nitrophenylacrylic acid, EtC6H4C(CO2H): CHC6H4NO2, from the aldehyde and the K salt, m. 138°, crystallized from C6H6-ligroin. Reduced with FeSO4 and NH4OH, the amino acid results, m. 150-50.5°. When diazotized and poured into H2SO4, or when the diazo solution is shaken with mol. Cu, a mixture of acids is obtained which is separated by crystallization from AcOH and then from C6H6-ligroin; 5-ethylphenanthrene-9-carboxylic acid is obtained as the insoluble fraction, m. 147-9°. From the mother liquor α-m-ethylphenyl-β-o-hydroxyphenylacrytic acid seps., m. 203° (decomposition).
Annalen der Chemie, Justus Liebigs published new progress about 112-63-0. 112-63-0 belongs to class esters-buliding-blocks, and the molecular formula is C19H34O2, Name: (9Z,12Z)-Methyl octadeca-9,12-dienoate.
Referemce:
Ester – Wikipedia,
Ester – an overview | ScienceDirect Topics