Patent GB-651268-A (GB)
Title: Process for the manufacture of fluoranthene derivatives
Filed: 1948-01-16
Abstract: 1 : 2-Dihydrofluoranthenes containing an unsubstituted or a substituted amino-alkyl group in the 1-position are prepared by reacting a 1 : 2-dihydrofluoroanthene or an alkyl derivative thereof except a 1-alkyl derivative having either a metal substituent in the 1-position or in the presence of a reactant capable of inserting a metal substituent in the 1-position, with an alkyl halide which contains a disubstituted amino group or a halogen atom, a hydroxyl group or a substituent convertible into an amino group by hydrolysis or reduction.  When necessary or desired the substituent capable of being converted into a substituted or unsubstituted amino group may be so converted, and when desired the product so obtained may be hydrogenated to the corresponding 1 : 2 : 3 : 4-tetrahydro compound. In addition the corresponding quarternary compounds may be formed by treatment with the usual quaternating agents.  The alkyl radical may have a straight or branched chain or may form part of a ring. Substituents in the amino group may be aliphatic, alicyclic, araliphatic or heterocyclic radicals.  Substituents which may be converted into the amino group by hydrolysis or reduction include acylamino and nitrile groups.  The following reaction components are specified chlorethyl diethylamine, chlorethyl-dibutylamine, chlorethyl-piperidine, chlorethyl-morpholine, chloropropyl - dimethylamine, bromopropyl - diethylamine, chlorisopropyl-dimethylamine, bromisopropyl-diethylamine, chlorobutyl-diethylamine, chloropentyl-piperidine, dimethylamino-cyclohexyl halides, halogen N-alkyl piperidines such as 3-chloro-N-methyl piperidine, 1-bromo-3-chloro - piperidine, 1 - chloro - 2 - oxyethane para toluic acid ester or chloracetonitrile. The alkylation is preferably carried out in an inert solvent such as toluene benzene xylene or nitrobenzene and in the presence of an inert gas such as nitrogen.  Agents which are capable of forming metal derivatives of 1 : 2-dihydrofluoranthene mentioned include alkali and alkaline earth metals, and their amides, hydrides, hydrocarbon compounds and alcoholates such as sodamide, sodium hydride, lithium butyl, potassium phenyl, lithium phenyl, potassium tertiary butylate, and potassium tertiary amylate.  The dihydrofluoranthenes obtained by the process of the invention may be hydrogenated to the corresponding 1 : 2 : 3 : 4-tetrahydro compounds which are identical with those described in Specification 630,704. In examples (1) a xylene solution of 2 : 2 : 4 - trimethyl - 1 : 2 - dihydrofluoranthene is treated with sodamide and then with b  - chlorethyl - dimethylamine to give 1 - (b  - dimethylamino - ethyl) - 2 : 2 : 4 - trimethyl - 1 : 2 - dihydrofluoranthene; (2) as in example (1) using b -chlorethyl-diethylamine to give the corresponding product.  Alternatively g -chloropropyl-piperidine may be employed.  A sample has been furnished under Sect. 2 (5) of 1 - (g - piperidino - propyl) - 2 : 2 : 4 - trimethyl - 1 : 2 - dihydro - fluoranthene made by treating a xylene solution of 2 : 2 : 4-trimethyl-1 : 2-dihydrofluoranthene first with sodamide and then with 1 - acetoxy - 3 - chloropropane, hydrolysing the product, treating with thionyl chloride and then with piperidine.